Multi-layer dry paint decorative laminate having discoloration prevention barrier

ABSTRACT

A decorative dry paint transfer laminate includes a layer of dry paint, a pressure-sensitive adhesive layer on one side of the dry paint layer, and a release liner in releasable contact with the dry paint layer on a side opposite from the pressure-sensitive adhesive (PSA). The release liner has a matte release coat layer that contacts the dry paint layer. The release liner is released from the dry paint layer after the PSA side is attached to a surface. The matte release coat adheres to the dry paint layer to provide a protective function but also to transfer a decorative matte finish to the dry paint layer when the release liner is removed from it. The laminate includes a barrier layer to protect against significant discoloration of the color in the dry paint layer caused by migration of mono azo pigments from a painted surface.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation-in-part of U.S. application Ser. No. 457,826,filed Jun. 9, 2003, which is a continuation-in-part of U.S. applicationSer. No. 367,611, filed Feb. 14, 2003. These applications areincorporated herein in their entirety by this reference.

FIELD OF THE INVENTION

This invention relates generally to dry paint transfer laminates, andmore particularly, to a multi-layer dry paint decorative laminate havinga barrier layer that inhibits migration of discoloration-causingpigments into color-producing layers of the laminate.

BACKGROUND

Dry paint transfer laminates have been used in the past as surfacecoverings that provide an alternative to conventional painting. Waterbased paints and oil based paints have well known shortcomings that canbe overcome by the use of decorative dry paint transfer films as a paintreplacement. Environmental problems such as solvent evaporation frompaint systems applied by spray painting also are avoided by use ofdecorative dry paint transfer films.

Such decorative dry paint transfer films are typically applied to asubstrate surface by an adhesive layer carried by the film. Use ofheat-activated adhesives or water-activated adhesives can have certaindisadvantages that are overcome by use of pressure-sensitive adhesives,by which the decorative film is adhered to the substrate surface byapplication of pressure only, typically at room temperature. Examples ofdecorative films having pressure-sensitive adhesive layers for interioror exterior applications are disclosed in U.S. Pat. No. 6,096,396 toPatton et al., U.S. Pat. No. 6,086,995 to Smith, and U.S. Pat. No.5,229,207 to Paquette et al.

Decorative films having a pressure-sensitive adhesives are often adaptedto facilitate application to a surface by using various forms ofrepositionable adhesives known in the art. The laminate can be initiallyapplied to a surface, removed temporarily, and then repositioned, toallow the adhesive to form a permanent bond. Decorative films havingsuch a repositionable adhesive layer are described, for example, in the'207 patent to Paquette et al.

The present invention comprises a multi-layer laminate adapted to beplaced in contact with a surface which can be a painted surface. Infilms overlaying painted surfaces containing pigmented materials such asdyes or mono azo pigments, the colored materials may migrate or bleedinto the overlaying film. This causes the finish to discolor. Pigmentsused in wall paints containing yellow pigments as a component, or to alesser extent, orange or red pigments or dyes, can contain such mono azoconstituents that can migrate from the wall surface through the overlaidfilm and into the color layer of the film, causing it to discolor.

The present invention provides a multi-layer laminate adapted forcontact with a painted substrate surface containing organic materialswith color constituents that will bleed or migrate; and the inventionaddresses a situation, in particular, where the painted surfacecontaining the migrating organic color components may not be modified toavoid the color migration problem. In response to this problem, theinvention provides a laminate containing one or more barrier layers thatcooperate to block or capture the migrating color materials, and inparticular, those containing mono azo pigments. The barrier layerinhibits discoloration of the colored layer or layers in the laminatecaused by the laminate contacting such a painted surface.

SUMMARY OF THE INVENTION

Briefly, the invention comprises a multi-layer laminate adapted toprovide a layer of color to a painted surface. The laminate includes apressure-sensitive adhesive for overlaying and contacting the paintedsurface. The laminate includes one or more barrier layers that slow orstop the migration of discoloration-causing pigments from the surface,through the adhesive layer, to the color layer of the laminate.

In one embodiment, the barrier will slow or stop the color change causedby mono azo pigments in interior latex paint. By applying a barrierlayer of specific polymers and/or by addition of specific additivematerials to the barrier layer, the color migration may be stopped orsignificantly reduced.

One embodiment of the invention comprises a decorative dry painttransfer laminate having a layer of dry paint, a pressure-sensitiveadhesive layer on one side of the dry paint layer, and a release linerin releasable contact with the dry paint layer on a side opposite fromthe pressure-sensitive adhesive. The dry paint layer comprises a binderand a pigment. A barrier layer is positioned between the dry paint layerand the pressure-sensitive adhesive layer. The release liner isremovable from the dry paint layer at room temperature. Thepressure-sensitive adhesive is adapted for adhering the laminate to asubstrate surface at room temperature. The substrate surface can be apainted wall surface containing organic materials with color that canbleed or migrate. The pressure-sensitive adhesive layer adheres thelaminate to the substrate surface under application of pressure. Therelease liner is then peeled away from the dry paint layer. The barrierlayer comprises a thin, flexible film made from a material that stops orappreciably reduces migration of discoloration-causing constituentsmigrating from the painted surface through the adhesive layer to thecolor layer. In one embodiment, the barrier layer can comprise apolymeric material having a cross-linking density sufficient to inhibittransmission of discoloration-causing pigments and/or a dispersedadditive that may capture or retard the migration ofdiscoloration-causing pigments. The barrier layer is particularly usefulin retarding or inhibiting the transmission of azo-type pigments and ispresent at a low coat weight or thickness which does not significantlyincrease the overall thickness of a decorative film. In one embodiment,the barrier thickness is no more than about 10% of the total thicknessof the decorative film (excluding the outer releasable carrier film).

These and other aspects of the invention will be more fully understoodby referring to the following detailed description and the accompanyingdrawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view illustrating one embodimentof a multi-layer dry paint transfer laminate according to principles ofthis invention.

FIG. 2 is a schematic illustration of the dry paint transfer laminateself-wound into a roll form.

FIG. 3 is a schematic cross-sectional view showing an alternativeembodiment of a dry paint layer contained in the laminate.

FIG. 4 is a schematic cross-sectional view showing another alternativeembodiment of the dry paint layer.

FIG. 5 is a schematic cross-sectional view illustrating an alternativeembodiment of the dry paint layer of FIG. 4.

FIG. 6 is a schematic cross-sectional view illustrating an embodimentcontaining a support layer.

FIG. 7 is a schematic cross-sectional view illustrating an embodimentcontaining a barrier layer.

FIG. 8 is a schematic illustration of a process for co-extruding asupport layer and an adhesive layer used in one embodiment of theinvention.

FIG. 9 is a schematic illustration of a process for co-extruding asupport layer and an adhesive layer used in another embodiment of theinvention.

FIG. 10 is a schematic view illustrating one embodiment of the inventionwhich includes a dry paint layer, a barrier layer and a tie coat for theadhesive layer.

DETAILED DESCRIPTION

Referring to FIG. 1, a multilayer dry paint transfer laminate 20 isadapted for use as a surfacing film. The multilayer laminate includes apigmented dry paint layer 22 comprising a synthetic resinous bindercontaining a dispersed pigment. The dry pigmented paint layer 22, alsoreferred to herein as a color layer, generally can be a monocoatpigmented layer as illustrated in FIG. 1, or it can be combined withadditional pigmented paint layers, coatings or print coats describedbelow. In each instance, these decorative elements of the multilayer drypaint transfer film will be referred to generally as a decorative drypaint layer. In the illustrated FIG. 1 embodiment, the dry paint layer22 has an upper surface 24 and a lower surface 26. The multilayerlaminate further includes a dry adhesive layer 28 overlying and adheredto the upper surface 24 of the dry paint layer, and a flexible andfoldable release liner 30 overlying and releasably adhered to the lowersurface of the dry paint layer. The release liner has a matte releasecoat 32 on its inner surface for releasably adhering the release liner30 to the lower surface 26 of the dry paint layer 22. The release liner30 is adapted to be peeled away from the dry paint layer under anapplied release force, also referred to herein as a carrier releasefunction. The matte release coat 32 separates from the dry paint layer22 but remains adhered to the release liner 30 when the release liner ispeeled away from the dry paint layer. The release liner 30 also has anadhesive release coat layer 34 on a surface opposite from the dry paintlayer. An exposed outer surface 38 of the adhesive release coat layer 34is adapted for releasably contacting an exposed outer surface 40 of theadhesive layer 28 when the laminate is wound in a roll form illustratedin FIG. 2.

Referring to FIG. 2, the dry paint transfer laminate 20 is self-woundinto a roll form with the outer exposed surface 38 of the adhesiverelease coat layer 34 in releasable contact with the exposed outersurface 40 of the adhesive layer 28. Thus, when the dry paint transferlaminate 20 illustrated in FIG. 2 is unwound, the adhesive release coatlayer 34 on the release liner separates from the outer surface 40 of theadhesive layer 28 and remains adhered to the release liner 30. The matterelease coat 32 remains adhered to the dry paint layer.

FIG. 3 illustrates a dry paint transfer laminate 42 which is identicalto the dry paint transfer laminate 20 illustrated in FIG. 1, except thatthe decorative dry paint layer includes an optically transparentsynthetic resinous clear coat layer 44 adhered to the lower surface 26of the pigmented dry paint layer 22. In this embodiment, the outer clearcoat layer 44 is in releasable contact with the matte release coat 32 ofthe release liner 30. When the release liner 30 is peeled away from theclear coat layer 44, the matte release coat 32 separates from the clearcoat layer 44 and remains adhered to the release liner 30.

FIG. 4 illustrates a multilayer dry paint transfer laminate 46 which isidentical to the dry paint transfer laminate 42 illustrated at FIG. 3,except that the decorative dry paint layer further includes a decorativeprint coat layer 48 between the pigmented dry paint layer 22 and theclear coat layer 44. The decorative print coat layer provides adecorative print pattern, and the pigmented dry paint layer 22 providesa background color and opacity for the decorative dry paint layer. Theprint pattern and background color are visible through the outer clearcoat layer 44.

FIG. 5 illustrates a multilayer dry paint transfer laminate 50 which isidentical to the dry paint transfer laminate 46 illustrated in FIG. 4,except that a second decorative print coat layer 52 can be printed orcoated between the print coat layer 48 and the outer clear coat layer44.

Additional print coat layers may be used. For instance, the multilayerlaminate may contain up to about five or more print coats, and in oneembodiment, preferably three or four print coat layers are used. Thelayers may have a print or design pattern using conventional printingmethods, such as gravure, flexography, silk screen, or ink jet printing.

FIG. 6 illustrates an embodiment of a multilayer dry paint transferlaminate 54 which is identical to the multilayer laminate 20 illustratedin FIG. 1, except that the laminate 54 includes a flexible reinforcinglayer 56 (also referred to herein as a support layer) between the drypaint layer 22 and the adhesive layer 28. The reinforcing layer 56provides a means of structural support for the decorative dry paintlayer and can provide additional opacity for the decorative dry paintlayer. The reinforcing layer has a tensile strength which exceeds thatof the dry paint layer or layers.

FIG. 7 illustrates another embodiment of the dry paint transfer laminate58 which is identical to the laminate 20 illustrated in FIG. 1, exceptthat the laminate 58 includes a flexible barrier layer 60 between thepigmented dry paint layer 22 and the adhesive layer 28. The interveningbarrier layer can be used to inhibit or prevent undesired migration ofconstituents between the adhesive layer and the paint coat layer. Suchbarrier properties can include reducing or avoiding undesireddiscoloration by inhibiting or preventing migration of pigments from anunderlying substrate surface through the adhesive layer to the dry paintlayer.

The embodiment of FIGS. 6 and 7 show separate support (reinforcing) andbarrier layers. In addition, the barrier layer 60 may be included as alayer in the FIG. 6 embodiment. In this instance, the barrier layer maybe applied between the dry paint layer and the support (reinforcing)layer, or the barrier layer may be applied between the adhesive layerand the support layer.

The dry paint layer 22 may have a thickness generally of about 0.5 toabout 1.5 mils, in one embodiment about 0.5 to about 1.2 mils, and inanother embodiment from about 0.5 to about 0.9 mil. The thickness of theadhesive layer may range generally from about 0.4 to about one mil, inone embodiment from about 0.4 to about 0.8 mil, and in anotherembodiment from about 0.4 to about 0.6 mil. The thickness of the releaseliner may range generally from about 0.5 to about 2 mils, in oneembodiment from about 0.5 to about 1.5 mils, and in another embodimentfrom about 0.85 to about 1.05 mils. The thickness of the matte releasecoat layer may range generally from about 0.05 to about 0.3 mil, and inone embodiment from about 0.1 to about 0.2 mil. The thickness of theadhesive release coat layer may range from about 0.04 to about 0.2 mil,in one embodiment from about 0.04 to about 0.15 mil, and in anotherembodiment from about 0.04 to about 0.08 mil. The thickness of the outerclear coat layer may range generally from about 0.05 to from about 0.4mil, and in one embodiment from about 0.05 to about 0.3 mil.

The thickness of the decorative print coat layers may range from about0.02 to about 0.15 mil, and in one embodiment from about 0.02 to about0.08 mils.

The reinforcing layer may have a thickness generally of about 0.3 toabout 1.4 mils. In one embodiment the thickness can be about 0.3 toabout 1.1 mils, in another embodiment about 0.3 to about 0.8 mil, and ina further embodiment about 0.3 to about 0.5 mil. When the reinforcinglayer is used, the overall thickness of the combination of the dry paintlayer and the support layer may be in the range of about 0.5 to about1.5 mils, in another embodiment about 0.5 to about 1.2 mils, and in afurther embodiment from about 0.5 to about 0.9 mil.

The barrier layer may have a thickness in the range of about 0.01 toabout 0.1 mil, and in one embodiment about 0.05 to about 0.1 mil, and inanother embodiment from about 0.01 to about 0.02 mil.

Each of the foregoing thicknesses are dry film thicknesses. Thelaminates may have any width or length that is suitable for its end use.For example, the width may range from about one to about 200 cm, and inone embodiment from 10 to 100 cm, and in another embodiment from about30 to about 40 cm. The length may range from about 10 to about 6500meters, and in one embodiment from about 15 to about 1000 meters. Thelaminates may take the form of flat sheets or as a self-wound roll formas illustrated in FIG. 2.

Dry Paint Layer

The dry paint layers may comprise independently one or more polymericbinders or resins, and one or more pigments. The reinforcing layer andbarrier layer may comprise one or more polymeric binders or resins, andoptionally one or more pigments. The transparent outer clear coat layermay comprise one or more polymeric binders or resins. These layers maybe made from solvent cast liquid coating or paint compositionscomprising the one or more binders or resins and one or more pigments(if used). These compositions may be dispersed in water or one or moreorganic solvents, and optionally may contain one or more additionaladditives for controlling properties such as rheological properties orbarrier properties. The dry paint layers, or the transparent outer clearcoat layer, or the reinforcing layer or barrier layer may each compriseindependently one or more extruded layers.

The binder or resin may comprise any binder or resin conventionally usedin coating or paint formulations. The binder may comprise athermoplastic or thermosetting resin. The binder or resin may be asynthetic resin or a natural resin. The binder or resin may comprise afilm forming material which may be cast as a solvent-based coating or inone embodiment may be an extrudable film forming material. Examples ofuseful binders or resins generally include acrylic, vinyl, polyester,alkyd, butadiene, styrene, urethane and epoxy resins and phthalic acidor anhydride resins, and mixtures thereof. More specifically, the binderor resin may include one or more polystyrenes, polyolefins, polyamides,polyesters, polycarbonates, polyvinyl chloride, polyvinyl alcohol,polyethylene vinyl alcohol, polyurethanes, polyacrylates, polyvinylacetates, ionomer resins, and mixtures thereof.

The binder or resin may comprise vinyl and vinylidene polymers orcopolymers containing units such as vinyl acetate, vinyl chloride, andvinylidene chloride; hydrocarbon polymers and copolymers containingethylene or propylene units and oxygenated or halogenated derivatives ofether, butadiene, oxygenated butadiene, isoprene, oxygenated isoprene,butadiene-styrene, butadiene vinyl toluene, and isoprene-styrene;polymers or copolymers containing units of acrylic acid, methacrylicacid, their esters, or acrylonitrile; vinylic hydrocarbon monomersreacted with unsaturated materials such as the reaction product ofmaleic acid or anhydride with styrene; and, broadly, various otherresinous rubber-like elastomeric latex polymers and copolymers ofethylenically unsaturated monomers and polymers obtainable in stableaqueous latex form. The binder or resin may comprise a copolymer ofvinyl chloride and vinyl acetate.

The polyolefins may be characterized as having a melt index or melt flowrate of less than about 30, and in one embodiment less than about 20,and in one embodiment less than about 10 as determined by ASTM TestMethod 1238. The polyolefins include polymers and copolymers ofethylene, propylene, 1-butene, etc., or blends of mixtures of suchpolymers and copolymers.

Various polyethylenes may be used including low, medium, and highdensity polyethylenes. The low density range for the polyethylenes maybe from about 0.910 to about 0.925 g/cm³, the medium density range maybe from about 0.925 to about 0.940 g/cm³, and the high density range maybe from about 0.940 to about 0.965 g/cm³. An example of a useful lowdensity polyethylene is Rexene 1017 available from Huntsman.

The propylene homopolymers which may be used either alone or incombination with a propylene copolymer include a variety of propylenehomopolymers such as those having melt flow rates from about 0.5 toabout 20 as determined by ASTM Test D 1238, condition L.

The polyamide resins include resins available from EMS American GrilonInc., Sumter, S.C. under the general tradename Grivory such as CF-65,CR-9, XE-3303 and G-21. The polyamide resins also include thoseavailable from, for example, Union Camp of Wayne, N.J. under the Uni-Rezproduct line, and dimer-based polyamide resins available from Bostik,Emery, Fuller, and Henkel (under the Versamid product line).

The polystyrenes include homopolymers as well as copolymers of styreneand substituted styrene such as alpha-methyl styrene. Examples ofstyrene copolymers and terpolymers include: acrylonitrile-butene-styrene(ABS); styrene-acrylonitrile copolymers (SAN); styrene butadiene (SB);styrene-maleic anhydride (SMA); and styrene-methyl methacrylate (SMMA);etc.

The polyurethanes include aliphatic as well as aromatic polyurethanes.

The polyesters may be prepared from various glycols or polyols and oneor more aliphatic or aromatic carboxylic acids. Polyethyleneterephthalate (PET) and PETG (PET modified with cyclohexanedimethanol)are useful film forming materials which are available from a variety ofcommercial sources including Eastman. For example, Kodar 6763 is a PETGavailable from Eastman Chemical; Another useful polyester from DuPont isSelar PT-8307 which is polyethylene terephthalate.

Acrylate polymers and copolymers and alkylene vinyl acetate resins(e.g., EVA polymers) may be used. Examples include Escorene UL-7520(Exxon), a copolymer of ethylene with 19.3% vinyl acetate; Nucrell 699(DuPont), an ethylene copolymer containing 11% of methacrylic acid, etc.

Ionomer resins (polyolefins containing ionic bonding of molecularchains) may be used. Examples of ionomers include ionomeric ethylenecopolymers such as Surlyn 1706 (DuPont) and Surlyn 1702 from DuPont.

Polycarbonates also are useful, and these are available from the DowChemical Co. (Calibre) G.E. Plastics (Lexan) and Bayer (Makrolon).

The pigment may be any pigment used in making decorative coatings. Theseinclude opacifying pigments, such as titanium dioxide and zinc oxide, aswell as tinting pigments such as carbon black, yellow oxides, brownoxides, tan oxides, raw and burnt sienna or umber, chromium oxide green,phthalocyanine green, phthalocyanine blue, ultramarine blue, cadmiumpigments, and chromium pigments. The pigments include organic reds suchas azo reds, quinacridone red and perylene red as well as organicyellows such as diarylide yellow. Mixed metal oxide pigments may beused. Filler pigments such as clay, silica, talc, mica, woloastonitewood flour, barium sulfate, calcium carbonate, aluminum silicate, andthe like can be added as well in conventional amounts traditionally usedin coating and paint formulations.

The solvent may be an organic-based solvent, such as a ketone, ester,aliphatic compound, aromatic compound, alcohol, glycol, glycol ether,etc. These include methylethyl ketone, methylisobutyl ketone, ethylacetate, white spirits, alkanes, cycloalkanes, benzene, hydrocarbonsubstituted aromatic compounds (e.g., toluene, the xylenes, etc.),isoparaffinic solvents, and combinations of two or more thereof.Alternatively, water or a water-based solution may be used to form anaqueous emulsion with the binder or resin. Water-based solutions includewater-alcohol mixtures. The solvent or water is sufficiently volatile sothat when applied to a substrate, the solvent evaporates leaving behindthe binder or resin, pigment (if used), and any other additionalnon-volatile components.

Additional ingredients that may be used include wetting agents;plasticizers; suspension aids; thixotropic agents such as silica; waterrepellant additives such as polysiloxane compounds; fire retardantadditives; biocides; defoamers; and flow agents.

The pigment concentration for the liquid paint or coating compositionused to form the dry paint layers may range from about 10 to about 30%by weight, and in one embodiment about 13 to about 27% by weight. Thebinder or resin concentration may range from about 20 to about 40% byweight, and in one embodiment about 22 to about 37% by weight. The wateror organic solvent concentration may range from about 30 to about 70% byweight, and in one embodiment about 40 to about 60% by weight. Theadditional ingredients such as wetting agents, suspension agents, etc.,may have concentrations up to about 5% by weight. The coating or paintcompositions used in making the dry paint layers may have a pigment tobinder volume concentration in the range of about 5 to about 35%, and inone embodiment 10 to about 30%.

The liquid paint or coating compositions used for making the dry paintlayers may be blended using known techniques. The dry paint layer maycomprise a single coat or multiple coats of paint and is in the form ofa continuous layer, while the printed decorative layers mayindependently be in the form of continuous or discontinuous layers. Whenmultiple coats for the dry paint layer are used, each coat may have thesame or a different formulation. The print coats may have the same coloror a different color than the dry paint layer, or the print coats mayhave the same color, or they may have colors that are different fromeach other. The dry paint layer may be used to provide background colorwhile the print layers may be used to provide a desired pattern ordesign.

(a) Transparent Top Coat Layer

The transparent outer clear coat layer may comprise a single coatinglayer or multiple coats, and may comprise any of the resinous materialsdescribed above. When multiple coats are used, each coat may have thesame or a different formulation. As mentioned previously, the outerclear coat layer may be solvent cast (aqueous or organic solvent based)or the outer clear coat layer may be extruded. The outer clear coatlayer, in one embodiment, provides enhanced scuff resistance, stainresistance and/or recoatability to the dry paint film layer or layersunderlying it. Enhanced recoatability facilitates the subsequentapplication of another dry paint film layer or printed decorative layerover it, or the application of conventional paint or decorative drypaint films.

(b) Reinforcing or Support Layer

The reinforcing or support layer may be formed from any of the binder orresin materials described above. This layer may be formed from asolution or an emulsion and applied using any of the coating techniquesdescribed below. This layer also may be extruded. The reinforcing layermay contain one or more of the above-described pigments to enhanceopacity of the finished laminate. The concentration of pigment in thereinforcing layer, when used, may range up to about 10% by weight, andin one embodiment about 6 to about 10% by weight.

The dry paint layers, outer clear coat layer or reinforcing layerindependently may contain inorganic fillers or other organic orinorganic additives to provide desired properties such as appearanceproperties (clear, opaque or colored films), durability and processingcharacteristics. Examples of useful materials include calcium carbonate,titanium dioxide, metal particles, fibers, flame retardants, antioxidantcompounds, heat stabilizers, light stabilizers, ultraviolet lightstabilizers, antiblocking agents, processing aids, and acid acceptors.

One or more of the dry paint layers, outer clear coat layer orreinforcing layer may contain a minor amount of an adhesive resin toenhance the adhesion of the dry paint layer to the outer clear coatlayer and/or the support layer. Also, or alternatively, tie coat layersof an adhesive resin can be used between the dry paint layers and eitherthe outer clear coat layer or the reinforcing layer. The adhesive resinfor the tie coat can be an acrylic resin adhesive, or it can be anethylene/vinyl acetate copolymer adhesive such as those available fromDuPont under the tradename Elvax. The adhesive resins available fromDuPont under the tradename Bynel also may be used.

In one embodiment, the dry paint layers, the outer clear coat layerand/or the reinforcing layer are flexible, but non-stretchable andnon-elastic at room temperature.

Adhesive Layer

The dry adhesive layer may comprise a pressure-sensitive adhesive (PSA)which bonds the decorative laminate to a substrate surface, underapplied pressure, at room temperature. The adhesive layer may be acontinuous or discontinuous layer, and it may comprise one or a mixtureof two or more adhesives. The adhesive layer may be a patterned adhesivelayer with relatively strong adhesive tack level in some areas and arelatively weak adhesive in other areas.

In one embodiment, the adhesive layer is a repositionable adhesive,having a low initial tack that allows slight movement of the laminate toallow positioning adjustments prior to forming a permanent bond. In oneembodiment, the adhesive has a suppressed initial level of tack at roomtemperature that allows the laminate to adhere to a substrate surfaceand be repositioned thereon followed by removal of the matte releaseliner from the decorative dry paint layer. The adhesive layer undergoesa subsequent buildup of adhesion due to the passage of time sufficientto permanently bond the dry paint layer to the substrate. In oneembodiment, the adhesive layer is characterized by producing only alimited amount of ooze beyond the borders of the laminate when thelaminate is applied to a substrate. In one embodiment, no ooze isproduced.

In one embodiment of the invention described below, thepressure-sensitive adhesive comprises a cross-linked acrylic resinousmaterial, and more particularly, a cross-linked acrylic emulsion. Aparticularly useful adhesive material comprises an internallycross-linked acrylic emulsion. These pressure-sensitive adhesivematerials provide a useful combination of low tack, peel and flowproperties with a sufficient level of cohesive strength at a useful(thin) coat weight for providing the differential release propertiesdescribed below. High molecular weight acrylic adhesives and externallycross-linked acrylic adhesives also may be used to produce the desiredcombination of functional properties.

The adhesive may comprise a rubber based adhesive, acrylic adhesive,vinyl ether adhesive, silicone adhesive, or mixture of two or morethereof. The adhesive may be applied to the laminate as a hot melt,solvent-based or water based adhesive. The adhesive materials that areuseful may contain as a major constituent an adhesive polymer such as anacrylic-type polymer; block copolymer; natural, reclaimed, orstyrene-butadiene rubber; tackified natural or synthetic rubber; acopolymer of ethylene and vinyl acetate; an ethylene-vinyl-acrylicterpolymer; polyisobutylene; or poly(vinyl ether). Other materials maybe included in the adhesive such as tackifying resins, plasticizers,antioxidants, fillers, and waxes.

A description of useful pressure-sensitive adhesives may be found inEncyclopedia of Polymer Science and Engineering, Vol. 13.Wiley-Interscience Publishers (New York, 1988). Additional descriptionof useful pressure-sensitive adhesives may be found in Encyclopedia ofPolymer Science and Technology, Vol. 1, Interscience Publishers (NewYork, 1964).

Pressure-sensitive adhesives that may be used include the hot meltpressure-sensitive adhesives available from H.B. Fuller Company, St.Paul, Minn. as HM-1597, HL-2207-X, HL-2115-X, HL-2193-X. Other usefulpressure-sensitive adhesives include those available from CenturyAdhesives Corporation, Columbus, Ohio.

Conventional PSAs, including silicone-based PSAs, rubber-based PSAs, andacrylic-based PSAs are useful. Another commercial example of a hot meltadhesive is H2187-01, sold by Ato Findley, Inc., of Wauwatusa, Wis. Inaddition, rubber based block copolymer PSAs described in U.S. Pat. No.3,239,478 to Harlan also can be used. This patent is incorporated byreference for its disclosure of such hot melt adhesives.

The adhesive compositions may contain at least one solid tackifier resincomponent. A solid tackifier is defined herein as one having a softeningpoint above 80° C. When the solid tackifier resin component is present,the adhesive compositions may comprise from about 40% to about 80% byweight of a thermoplastic elastomer component, in one embodiment fromabout 20% to about 60% by weight, and in another embodiment from about55% to about 65% by weight of a solid tackifier resin component. Thesolid tackifier reduces the modulus of the mixture sufficiently to buildtack or adhesion. Also, solid tackifiers (particularly the highermolecular weight solid tackifiers (e.g., Mw greater than about 2000) andthose having a lower dispersity (Mw/Mn=less than about 3) may be lesssensitive to migration into the polymer film layer. This is desirablesince migration of tackifier into the film layer may cause dimensionalinstability.

The solid tackifier resins include hydrocarbon resins, rosin,hydrogenated rosin, rosin esters, polyterpene resins, and other resinswhich exhibit the proper balance of properties. A variety of usefulsolid tackifier resins are available commercially such as terpene resinswhich are sold under the trademark Zonatac by Arizona Chemical Company,petroleum hydrocarbons resins such as the resins sold under thetrademark Escorez by Exxon Chemical Company, or Wingtack 95, a synthetictackifier resin available from Goodyear, Akron, Ohio.

The modulus of adhesive mixtures to be coextruded also may be lowered bythe incorporation of liquid rubbers, i.e., liquid at room temperature.The liquid rubbers generally will have an Mw of at least 5,000 and moreoften at least 20,000. Incorporation of liquid rubbers in amounts ofless than 10%, and even less than 5% by weight based on the overallweight of the adhesive formulation results in adhesives which arecoextrudable with the polymeric film materials. The incorporation of aliquid rubber may produce an adhesive having increased tack andadhesion. Liquid block copolymers such as liquid styrene-isoprene blockcopolymers may be used. Other liquid rubbers which may be incorporatedinto the adhesive mixture include liquid styrene-butadiene rubbers,liquid butadiene rubbers, ethylene-propylene rubbers, etc.

The adhesive layer also may contain one or more pigments to enhance theopacity of the paint film layers overlying it and permit use of thinnerpaint film layers to achieve desired levels of opacity. Any of thepigments identified above may be used. Examples include titanium dioxideand carbon black. The pigment volume concentration may range up to about10%, in one embodiment from about 5% to about 10%, and in anotherembodiment from about 2% to about 8%.

The adhesive compositions also may include other materials such asantioxidants, heat and light stabilizers, ultraviolet light absorbers,fillers, colorants, antiblocking agents, reinforcing agents, andprocessing aids.

The adhesive compositions may contain inorganic fillers and otherorganic and inorganic additives to provide desired properties. Examplesof useful fillers include calcium carbonate, titanium dioxide, metalparticles, and fibers.

Barrier Layer

The barrier layer may comprise any of the acrylate polymers orcopolymers described above, polyvinyl alcohol, copolymers derived fromethylene and vinyl acetate, and copolymers derived from ethylene, vinylacetate and polyvinyl alcohol. The barrier layer may comprise a polymerblend derived from polyvinyl alcohol, urethane, Cymel 385 (a product ofCytec identified as a melamine formaldehyde resin) and a polyaziridine(e.g., NeoCryl CX100 which is identified as trimethol-tris N (methylaziridinyl) proprionate and is available from Avecia Resins), the weightration of polyvinyl alcohol to urethane in one embodiment being about20:80. The following examples illustrate specific coating compositionswhich may be used in forming the barrier layer: Percent by WeightBarrier Layer No. 1 Elvacite 2042 (product of Ineos 20 identified as anethyl methacrylate copolymer) Tolune 48 Methyl ethyl ketone 32 BarrierLayer No. 2 Adcoat 61WG178 (product of Rohm and Haas 55.55 identified asa solution of acrylic polymer) Syloid 234 (product of Grace Davidson0.10 identified as synthetic amorphous silica) N-propanol 44.35 BarrierLayer No. 3 Adcoat 74.07 N-propanol 25.83 Syloid 234 0.10 Barrier LayerNo. 4 Adcoat 61WG178 55.55 N-propanol 44.35 Syloid 234 0.10 Desmodur CB75N (product of Bayer 0.44 identified as an oligomeric toluenediisocyanate) Barrier Layer No. 5 Adcoat 61WG178 74.07 N-propanol 25.83Syloid 234 0.10 Desmodur CB 75N 0.44 Barrier Layer No. 6 Adcoat 61WG17858.0 R-900 TiO₂ (product of DuPont identified 15.00 as rutile titaniumdioxide) N-propanol 24.0 Isobutanol 3.00 Barrier Layer No. 7 Adcoat61WG178 58.00 R-900 TiO₂ 15.00 N-propanol 24.00 Isobutanol 3.00 DesmodurCB 75N 0.88 Barrier Layer No. 8 Air Vol 523 (product of Air Products 5.0identified as polyvinyl alcohol) Water 47.5 Isopropanol 47.5

As mentioned previously, the substrate surface contacted by thedecorative laminate can comprise a painted surface having pigmentmaterials containing color constituents which can migrate into thedecorative film and through the adhesive layer to the color layer,causing discoloration. The barrier layer stops or retards thetransmission of undesired discoloration-causing pigments sufficient tomaintain discoloration or color shift of the color layer to within alevel which is essentially unnoticeable for a useful life of thedecorative film. Normal use conditions under which the decorative filmis applied and normally in use are defined as temperatures from about 4°C. (40° F.) to about 35° C. (90° F.), and more particularly, from about15° C. (60° F.) to about 27° C. (80° F.). To approximate the amount ofcolor shift that may occur during an estimated useful life of the filmunder normal use conditions, film samples are tested by acceleratedaging techniques and measured for color shift under those conditions.(Higher temperatures accelerate migration of discoloration colorconstituents.) In one embodiment, color shift is measured by comparingthe color of an interior latex test sample with an interior latex colorstandard and then subjecting the test sample to a 60° C. (140° F.)environment for approximately 400 hours (16 days). The test sample isthen measured for color shift and compared with the standard todetermine the amount of color shift. According to one test, color shiftis measured under ASTM 805 test procedures, and the unit of measure isC.I.E. color units on the Δb* (yellow/blue) scale, although other colorshift measurements can be used to determine whether color shift iswithin a specified range. These color shift measuring techniques areuseful in evaluating whether a color shift is acceptably low bymeasuring the color shift in a blue painted sample caused by migrationof yellow color constituents from mono azo pigments or dyes. In oneembodiment, the color shift is considered sufficiently low to be withinan acceptable range if testing at 60° C. for 400 hours produces a colorshift equal to or less than about 0.30 C.I.E. Δb* color units.

The barrier layer comprises a thin, flexible polymeric film which, inone embodiment, can be cross-linked to enhance barrier properties. Oneembodiment of the barrier layer comprises a non-pigmented acrylicresinous material which is cross-linked at a cross-linking densitysufficient to retard transmission of mono azo pigments to within theacceptable level. One embodiment of this barrier layer comprises arelatively low molecular weight acrylic polymer which is cross-linkedwith a melamine resin. A low molecular weight acrylic resin suitable forthe barrier layer has a molecular weight below about 100,000. One suchcross-linked acrylic barrier layer (identified in more detail in Example9) is the acrylic polymer (Adcoat 61WG178 from Rohm and Haas) which hasa molecular weight of about 50,000. The cross-linking increases themolecular weight and raises the softening point of the barrier coat andcreates a network at the molecular level that retards transmission ofthe azo color constituents through the barrier layer.

The use of a cross-linked polymeric material as a barrier coat can beuseful in producing the desired retardation, but in some instances, thecross-linking of the resinous material can reduce adhesion to the PSAlayer. In some instances, it is desirable to include a tie coat betweenthe base coat and the PSA layer. One tie coat layer which has been shownto improve adhesion comprises a thin coating of a material similar tothe pigmented base coat layer used in the decorative film. One exampleof such a tie coat is the plasticized vinyl tie coat shown in Example 9.

The PSA layer can be applied to the barrier coat by direct coating orcasting of the PSA onto the previously formed barrier coat.Alternatively, the PSA can be separately cast on a temporary carrier andthen transfer-laminated from the carrier to the barrier coat.Experimental tests have shown that adhesion between the barrier coatingand the adhesive and the resistance to migration of color constituentsis better when the adhesive is coated directly onto the barrier coatingas opposed to transfer-lamination of the cast adhesive.

In another embodiment, the barrier layer can be made from athermoplastic (non-cross linked or lightly cross linked) polymericmaterial. One such material is the low molecular weight acrylic material(61WG178) described above. To increase the material's resistance tomigration of color constituents, a fine particulate filler material oradditive can be dispersed in the barrier material. The filler oradditive can have scavenging properties, or properties similar to alaking agent to which migrating pigments can attach, or the fillermaterial can physically retard transmission rate to a sufficiently lowlevel. Materials that have been found to reduce, capture, or stopmigration of mono azo pigments include fumed aluminum oxide, metalphosphate compounds and/or titanium dioxide, although other metal salts,or oxides, or metal compounds also can be used to produce similarresults. One metal compound useful in the barrier coat comprises analuminum zirconium phosphosilicate available as Xtain A from Halox.Tests have shown good color shift results for low molecular weightthermoplastic acrylic resinous barrier materials containing these typesof filler or additive materials. These materials also reduce color shiftin a cross-linked acrylic resinous barrier coat layer.

In one embodiment of the invention, in which the barrier coat comprisesa thermoplastic resinous material containing a dispersed filler forretarding color transmission, adhesion to the PSA layer can be enhancedby addition of a dispersed adhesion agent to the barrier coat. The lowmolecular weight thermoplastic acrylic barrier coat can have adhesionproperties enhanced by addition of polyvinyl pyrrolidone homopolymer(PVP). This barrier coat produces good adhesion to PSA layers which areeither direct-coated or transfer-laminated to the barrier coat. The PVPis compatible with the acrylic base polymer material and the solventsused in the system and also increases adhesion to the PSA layer. Onesource of the PVP is International Specialty Products (ISP) identifiedas PVP K80.

Another embodiment of the barrier layer comprises a thermoplasticpolymeric material having a sufficiently high molecular weight to retardcolor transmission to within desirable limits. A suitable high molecularweight barrier material has a molecular weight in excess of 250,000. Onebarrier material comprises a high molecular weight acrylic resinousmaterial such as a polymethyl methacrylate (PMMA) having a molecularweight of about 350,000. This barrier material can produce theacceptable color shift results without addition of adhesion promoters oradditives and also can be used without an additional tie coat layer topromote adhesion to the PSA.

The barrier layer of this invention is applied at a sufficiently lowcoat weight to produce a dry film thickness within a range of about 0.05to about 0.20 mil. The barrier coat is sufficiently thin so as to notadd significant thickness to the decorative portion (excluding therelease liner) of the multi-layer laminate. In one embodiment, filmthickness of the barrier layer is not more than about ten percent (10%)of the total thickness of the decorative portion of the film.

The barrier layer also is resistant to softening at elevatedtemperatures, and in one embodiment, the barrier layer has a glasstransition temperature (T_(g)) greater than about 60° C.

The addition of the barrier layer and the adjoining tie coat layer (ifused) does not impact the differential release properties of thedecorative film. Adhesion of the barrier layer to the PSA layer issufficient to not appreciably reduce the peel force characteristics ofthe laminate in its self-wound form as described herein.

Matte Release Liner

The release liner may independently comprise paper, polymer film, or acombination thereof. The release liner, in one embodiment, is thermallystable, non-elastomeric and non-stretchable at room temperature.

Although paper of any weight may be used as a release liner, paperhaving weights in the range of from about 30 to about 120 pounds perream are useful, and papers having weights in the range of from about 60to about 100 pounds per ream are preferred. The term “ream” as usedherein equals 3000 square feet.

Alternatively, the release liner may independently comprise a polymericfilm, and examples of polymeric films include polyolefin, polyester, andcombinations thereof. The release liner preferably may be formed from aflexible, foldable, heat-resistant, substantially inelastic,self-supporting temporary carrier film or casting sheet as is known inthe art of dry paint transfer films. The release liner is preferably anoriented polyester film such as polyethylene terephthalate (PET)available as Mylar, a trademark of DuPont, or Hoechst Celanese Hostaphan2000 polyester film, for example.

The release liner provides structural integrity to the laminate untilthe liner is removed upon application of the laminate to a substratesurface.

The matte release coat layer may comprise any of the above identifiedbinders or resins which provide a level of tack or adherence between therelease coat layer and the decorative dry paint layer, which maycomprise either the color coat layer, the outer clear coat layer, or thedecorative print layer. The tack level of the matte release coat layeris sufficient to prevent separation of the release coat layer from theadhered dry paint layer during the process of forming the dry painttransfer laminate and during normal handling of the laminate, includingforming it in its self-wound orientation, unwinding it, and applying itto the substrate surface. The matte release coat also continues to havesufficient release properties to facilitate separation between therelease coat layer and the adhered dry paint layer after having appliedthe laminate to the substrate.

The matte release coat formulation comprises a coating which can beapplied to the release liner by conventional casting techniques such asgravine printing. The preferred coating composition is a thermosettingresinous material which, when exposed to heat for drying it, also crosslinks and permanently bonds as a surface film adhered to the releaseliner. The solids contained in the matte release coat preferablyinclude, as a principal component, one or more crosslinking agents toprovide good adhesion of the dried crosslinked coating to a polyestercarrier film. In one embodiment, the matte release coat formulationincludes a primary crosslinking resin such as a melamine resin thatcontrols crosslinking and produces adhesion to the polyester carrierfilm. A presently preferred crosslinking resin is hexamethoxy methylresin such as Cymel 303. A suitable primary functional resin is a vinylresin such as a medium molecular weight vinyl chloride-vinyl acetateresin known as VAGH. The vinyl resin can be present in an amount up toabout 20% of the total solids in the matte release coat. In addition,the matte release coat can include a secondary functional resin toimprove release of the top surface of the decorative dry paint layerfrom the matte release coat. In one embodiment, the secondary functionalresin can be an acrylic-modified alkyd resin such as the resin known asChempol 13 1501 or Lankyd 13-1245. This secondary functional resincomprises from about one percent to about 16% of the total solids, byweight, of the matte release coat. The matte release coat furtherincludes a suitable catalyst for accelerating the crosslinking process,typically comprising from about one percent to about eight percent ofthe total solids in the matte release coat, by weight.

The resinous components of the matte release coat composition arecombined with suitable solvents. In one embodiment, the resins are mixedwith a primary resin solvent such as methyl isobutyl ketone (MIBK) whichcomprises from about 65% to about 85% of the total solvent in theformulation. A secondary resin solvent, such as isopropyl alcohol(IPOH), is useful in retarding crosslinking of resins in solution. Thesecondary resin solvent preferably comprises from about 5% to about 20%of the total solvent.

The matte release coat formulation is prepared by dissolving the primaryfunctional resin in the primary and secondary resin solvents by mixingand then adding the secondary functional resin together with a primarymatting agent, preferably in the form of a filler comprising a fineparticulate inert inorganic material. In one embodiment, the fillercomprises aluminum silicate with an average particle size of about 4.8microns. In another embodiment, the filler can comprise talc. The fillercontained in the formulation comprises up to about 50% of the totalsolids in the matte release coat. In one embodiment, the talc fillermaterial comprises from about 40% to about 50% of the total solidscontained in the matte release coat. The fine particulate filler isthoroughly dispersed in the resin and resin solvent blend, preferablyunder elevated temperatures from about 100° F. to about 120° F.

In use, when the matte release layer dries and cross links, it forms achemical matte coating on the surface of the carrier sheet. The mattesurface is controlled by the amount and particle size of the filler. Thefine particles project through the dried exterior surface of the matterelease coat to form, on a microscopic scale, a surface with amicroroughness that transfers a replicated microroughness to the exposedsurface of the dried outer clear coat or dry paint layer. This produceslight scattering, resulting in a flat or low surface gloss matte finishon the top surface of the decorative dry paint layer.

In one embodiment a matte release coat formulation useful for thisinvention contains no significant amount of a silicone-based releasematerial and/or a wax-based component. Such materials may be useful inproviding release properties at high temperatures; but the matte releasecoat of this invention, in one embodiment, comprises a formulation that,in the absence of a silicone-based release material or a wax-basedcomponent, provides a useful combination of room temperature release,adherence of the release liner to the dry paint layer, and transfer ofthe matte surface to the exposed surface of the dry paint layer. Statedanother way, the matte release coat has a hardened state at roomtemperature and is made from a resinous material that contains (1) asurfacing component that forms a matte release surface, (2) an adhesioncomponent for releasably adhering the matte release surface to the drypaint layer, and (3) a release component that releases the matte releasesurface from contact with the dry paint layer at room temperature totransfer the matte surface finish from the matte release surface to theexposed surface of the dry paint layer.

In one embodiment, the matte release coat comprises, on a solids basis,from about 10% to about 30% by weight alkyd resin; from about 10% toabout 30% by weight vinyl resin; from about 20% to about 35% by weightmelamine crosslinking resin; and from about 5% to about 10% catalyst.The balance of the solids comprises the fine particulate filler, e.g.talc, as described previously.

In one embodiment, the weight ratio of particulates to resin or bindermay range up to about 1.1:1, in one embodiment from about 0.7:1 to about1.1:1, in another embodiment from about 0.7:1 to about 0.9:1, and in afurther embodiment from about 0.9:1 to about 1.1:1.

The gloss transferred to the outer surface of the dry paint layer can becontrolled by a combination of release coat formulations and thecomposition of the outer surface layer of dry paint in contact with therelease coat. In one embodiment, an 85° gloss of less than about 10gloss units can be transferred to dry paint films having a monocoat orbase coat/clear coat finish comprised of urethane, acrylic and/or vinylresinous paint layers. The preferred release coat comprises anacrylic/vinyl blend containing a micro-particle filler. In anotherembodiment, 85° gloss measurements of less than about 35 gloss units canbe transferred to dry paint films having a monocoat or base coat/clearcoat finish comprised of urethane, acrylic and/or vinyl resinous paintlayers. The preferred release coat comprises an acrylic modified alkydresin and/or vinyl resins containing dispersed microparticles.

The carrier film or release liner is typically contained on a supplyroll from which the carrier is unwound and passed to a gravure printstation where the matte release coat is coated onto the release liner.The release liner containing the matte release coat is then passedthrough a drying oven operated at a temperature from about 325° F. toabout 350° F., sufficient for drying and crosslinking the matte releasecoat. In the first stage drying oven, the matte release coat issufficiently cross-linked to permanently bond it to the carrier sheet.Preferably, the matte release coat is coated and dried to a coat weight(dry) from about 3 to about 6 gsm.

The adhesive release coat layer may comprise any release coatingcomposition known in the art. Silicone release coating compositions maybe used. The silicone release coating compositions typically comprisepolyorganosiloxanes such as polydimethylsiloxanes. The silicone releasecoating composition used in this invention may be room temperaturecured, thermally cured, or radiation cured. Generally, the roomtemperature and thermally curable compositions comprise at least onepolyorganosiloxane and at least one catalyst (or curing agent) for suchpolyorganosiloxane(s). These compositions may also contain at least onecure accelerator and/or adhesivity promoter.

Each of the layers in the multi-layer laminate may be independentlyapplied and dried and/or cured using known techniques. The applicationtechniques include gravure, reverse gravure, offset gravure, rollcoating, brushing, knife-over roll, metering rod, reverse roll coating,doctor knife, dipping, die coating, slot die coating, spraying, curtaincoating, slide coating, slide curtain coating, extrusion, co-extrusion,flexographic, letter press, rotary screen, and flat screen. In oneembodiment, the pressure sensitive adhesive layer may be applied usingtransfer lamination. The decorative print layers may be applied usingknown printing techniques including gravure, flexographic, silk screen,and ink jet printing. The applied layers may be dried and/or cured byexposure to heat or to known forms of ionizing or actinic non-ionizingradiation. Drying or curing temperatures that may be used may range fromabout 115° C. to about 160° C., and in one embodiment about 140° C. toabout 150° C. Useful types of radiation include ultraviolet light andelectron beam. The equipment for generating these forms of thermal orradiation drying and/or curing are well known to those skilled in theart.

Various layers of the multi-layer laminate also can be formed byextrusion and co-extrusion techniques identified above and described inmore detail in U.S. application Ser. No. 457,826 identified above andincorporated herein by reference. The dry paint layer or the supportlayer may be coextruded with the adhesive layer using separate extrudersas illustrated in FIG. 8 or a dual die extruder as illustrated in FIG.9. Referring to FIG. 8, release liner 70 is uncoiled from a roll 72 andadvanced past an extrusion die 74 where it is coated with an adhesivelayer 76, and then past an extrusion die 78 where a reinforcing orsupport layer 79 is coated onto the adhesive layer 76. The resultingco-extrudate is collected on a take-up roll 80. Referring to FIG. 9, therelease liner 70 is advanced past a dual extrusion die 82 whichsimultaneously coats the release liner 70 with a coextruded adhesivelayer 84 and support layer 86. The resulting co-extrudate is collectedon a take-up roll 88.

The dry paint transfer laminate illustrated in FIG. 1 may be made byapplying the adhesive release coat to the lower surface of the releaseliner using one of the foregoing application techniques and then curingthe release coat. The coat weight for the adhesive release coat layermay be in the range from about 0.1 to about one gram per square meter(gsm), and in one embodiment from about 0.25 to about 0.35 gsm. Thematte release coat layer is then applied to the upper surface of releaseliner using one of the above described application techniques (e.g.,gravure) and then dried or cured. The coat weight for the matte releasecoat may be in the range from about 2.5 to about 6.5 gsm, and in oneembodiment, from about 4.5 to about 5.5 gsm. The liquid paint or coatingcomposition for forming the pigmented dry paint layer is then applied tothe surface of the matte release coat layer using one of the abovedescribed application techniques (e.g., reverse roll or slot die) andthen dried or cured. The coat weight for the pigmented dry paint layermay range from about 20 to about 60 gsm, and in one embodiment about 30to about 40 gsm. One or more coats may be applied. Thepressure-sensitive adhesive layer is then applied to the upper surfaceof dry paint layer using one of the above indicated applicationtechniques (e.g., slot die) and then dried or cured. The pressuresensitive adhesive may be applied using coating techniques or transferlamination. The coat weight for the pressure sensitive adhesive layermay range from about 10 to about 30 gsm, and in one embodiment about 11to about 17 gsm. The dry paint transfer laminate 20 may then be woundinto roll form as illustrated in FIG. 2.

The dry paint transfer laminate illustrated in FIG. 3 may be made usingthe same procedure as the laminate 20 of FIG. 1, except that thetransparent outer clear coat layer is applied to the matte release coatlayer and then dried or cured prior to application of the pigmented drypaint film layer. The dry paint layer is then applied to the surface ofthe clear coat layer. The clear coat layer may be applied using one ofthe foregoing application techniques (e.g., gravure). The coat weightfor the clear coat layer may range from about one to about 5 gsm, and inone embodiment about 2.5 to about 3.5 gsm. One or more coats may beapplied. The dry paint transfer laminate may then be wound into a rollas illustrated in FIG. 2.

The dry paint transfer laminate illustrated in FIG. 4 may be made usingthe same procedure used as the laminate 20, except that the liquid paintcomposition for forming the printed decorative layer is applied to thesurface of the transparent film layer and then cured prior toapplication of the dry paint film layer. The dry paint film layer isthen applied to the surface of the printed decorative layer. The printeddecorative layer may be applied using any of the foregoing printingtechniques (e.g., gravure, flexographic, silk screen, or ink jet). Thecoat weight for the printed decorative layer may range from about 0.3 toabout 2 gsm, and in one embodiment about 0.3 to about 0.7 gsm. The drypaint transfer laminate may then be wound into a roll as illustrated inFIG. 2.

The dry paint transfer laminate illustrated in FIG. 5 may be made usingthe same procedure as the laminate of FIG. 4, except that the liquidpaint composition for forming the second printed decorative layer isapplied to the surface of the transparent film layer and then dried orcured prior to the application of the first printed decorative layer.The second printed decorative layer may be applied using any of theforegoing printing techniques (e.g., gravure, flexographic, silk screen,ink jet). The coat weight for the second printed decorative layer mayrange from about 0.3 to about 2 gsm, and in one embodiment about 0.3 toabout 0.7 gsm. The dry paint transfer laminate may then be wound into aroll as illustrated in FIG. 2.

The dry paint transfer laminate illustrated in FIG. 6 may be made usingthe same procedure used for making the laminate 20 illustrated in FIG.1, except that the reinforcing layer is adhered to the dry paint layer.The reinforcing layer may be coextruded with the adhesive layer and thenthe dry paint film layer may be coated (e.g., gravure) onto thereinforcing layer. The dry paint transfer laminate may then be woundinto a roll as illustrated in FIG. 2.

The dry paint transfer laminate illustrated in FIG. 7 may be made usingthe same procedure used for making the laminate 20 illustrated in FIG.1, except that the barrier layer is coated on the dry paint transferlayer. The dry paint transfer laminate may then be wound into a roll asillustrated in FIG. 2.

The dry paint transfer laminate may be made in a single production lineor in multiple production lines or multiple production facilities. Withmultiple production lines or facilities, part of the laminate may beproduced as a roll laminate, dried or cured, rolled up, transferred tothe next production line or facility, unrolled, and further treated withthe application of additional layers. For example, the dry paint layerand the adhesive layer may be formed in multiple lines, or they may beformed in sequence in a single production line, or they may besimultaneously formed such as by coextrusion or multi-die coatingmethods.

The dry paint transfer laminate 20 may be used by unrolling the laminatefrom the roll illustrated in FIG. 2, and simultaneously applying thelaminate to the substrate surface to be covered. The substrate maycomprise any flat surface. The flat surface may comprise wall board,plastic sheet, metal sheet, composites, and the like. The substrate maycomprise an interior (i.e., indoor) surface or an exterior (i.e.,outdoor) surface. The laminate may be applied to a painted surfacehaving various surface finishes, from flat, semi-gloss to glossy. Thelaminate is placed over the substrate with the adhesive layer in contactwith the substrate. Pressure is applied, with repositioning ifnecessary, until the laminate is adhered to the surface. The releaseliner is then peeled off the front face of the decorative laminate,leaving the dry paint film layer adhered to the substrate by theadhesive layer. The dry paint transfer laminates shown in FIGS. 3through 7 and in FIG. 10 also may be applied to a substrate surface inthe same manner as the laminate 20.

Differential Release System

In one embodiment of the invention, the release properties of thelaminate are controlled so that, in the embodiments illustrated in FIGS.1-7 and FIG. 10, the release force required to separate the matterelease coat layer from the dry paint layer (which may comprise thetransparent layer, the color layer, or printed decorative layer) isgreater than the release force required to separate the adhesive releasecoat layer from the pressure-sensitive adhesive layer.

In one embodiment, the carrier release force required to separate thematte release coat layer from the dry paint layer (i.e., the colorlayer, the clear coat layer, or the printed decorative layer) may begenerally in the range from about 20 to about 180 grams per two inches(g/2 in), in one embodiment from 30 to about 150 g/2 in, and in anotherembodiment 40 to about 120 g/2 in. In other embodiments the releaseforce range may be from 50 to about 100 g/2 in, from 50 to about 90 g/2in, from about 70 to about 90 g/2 in, and from about 50 to about 65 g/2in.

In one embodiment, the unwind release force required to separate theadhesive release coat layer from the pressure-sensitive adhesive layeris generally in the range from about 10 to about 150 g/2 in, in oneembodiment from about 20 to about 150 g/2 in, in another embodimentabout 20 to about 90 g/2 in, and in other embodiments from about 30 toabout 150 g/2 in, about 30 to about 100 g/2 in, and about 30 to about 70g/2 in.

The test method for determining these release forces involves measuringthe force required to separate a two-inch wide release coated liner fromthe dry paint layer or from an adhesive coated substrate, with therelease coated liner extending at an angle of 90° relative to the layeror substrate and being pulled at a rate of 300 inches per minute. Thetest is conducted at room temperature.

According to one embodiment of the invention, the decorative filmcontains a differential release system which enables the film to beunrolled from its self-wound form with the release liner maintainingcontinuous contact with the dry paint layer. As the decorative film isunrolled, the silicone-coated outer surface of the release linerpreferentially releases from contact with the PSA side of the film whilethe matte release coat side of the release liner maintains constantcontact with the dry paint layer. This contact of the release liner withthe dry paint layer is maintained throughout unwinding, application tothe substrate surface, and any repositioning of the decorative film onthe surface, until the release liner is ready to be peeled away from thedecorative paint layer. The differential release system is adapted tomaintain such preferential contact between the release liner and the drypaint layer because the dry paint layer is non-self-supporting, i.e., ithas no structural integrity in and of itself, and therefore relies uponits contact with the release liner to provide the necessary structuralsupport during unrolling, handling and repositioning, for example.

As mentioned previously, the release force between the release liner andthe matte release layer (carrier release force) exceeds the releaseforce between the silicone-coated side of the releaser liner and the PSA(unwind release force). Tests have shown that this “force differential”is dependent upon the rate or speed at which the materials at eachinterface are peeled away from each other. Inasmuch as the self-woundfilm, in use, may be unwound at different speeds, an objective of thedifferential release system is to ensure that the carrier release forceexceeds the unwind release force over a wide range of release rates thatare normally encountered during use. Generally speaking, this forcedifferential is maintained over a wide range of speeds. During use, slowrates are encountered when unwinding a new roll or during the initialstart of a roll on the surface. Medium to fast rates are encounteredwhen the strip continues down the surface. In one embodiment, the forcedifferential is maintained for a range of speeds up to about 300 inchesper minute for a 2 inch wide strip. In another embodiment, this forcedifferential is maintained up to a speed of at least 600 inches perminute for a 2 inch wide strip.

The force needed to remove the PSA from the silicone side of the lineralso should be less than the force needed to peel the carrier off thedry paint side in order to prevent peeling the carrier during slittingor unwinding, in addition to avoiding peeling of the carrier duringunrolling, application to a surface, and repositioning on the surface.Unwind speeds in excess of 600 inches per minute may be encountered whencutting the film to individual roll sizes, but tests have shown that, inone embodiment, at such high speeds an undesired unwind response is notproduced even when unwind release forces exceed carrier release force.

Such differential release forces can be measured, as describedpreviously, by separating the liner from the matte release layer or thePSA layer in a two-inch wide strip at an angle of 90° pulled at a rateof 300 inches per minute with the tests conducted at room temperature.In one embodiment, the carrier release force is maintained higher thanthe unwind release force for release rates from about 6 inches perminute up to at least about 300 inches per minute. In anotherembodiment, the carrier release force is maintained within a range fromabout 45 to about 65 grams/2 inches over a wide range of release ratesfrom about 6 inches per minute up to at least about 300 inches perminute. A corresponding unwind release force is maintained within arange from about 20 to about 40 grams/2 inches, over a range of linerrelease rates from about 12 to about 60 inches per minute.

Tests have shown that carrier release forces are maintained at arelatively uniform level across a wide range of release rates, whereasunwind release forces tend to increase as release rates increase and caneventually exceed the carrier release forces above certain higherrelease rate levels. However, tests have shown that for release ratesabove about 300 inches per minute, an unwind release force in excess ofthe carrier release force does not negatively impact premature releaseof the release liner from the matte release layer during normal useconditions of the self-wound decorative film.

The composition of the PSA is coordinated with the composition of thedry paint layer in order to produce the desired differential releaseproperties. The particular formulation used for the PSA can affectunwind release response. In addition, the composition of the dry paintlayer which comes into contact with the matte release layer can affectrelease properties. In one embodiment, a relatively low unwind releaseforce can be desirable if the carrier release force is relativelyhigher. However, there are limitations on the absolute magnitude of thecarrier release force. Producing a substantially higher carrier releaseforce compared to the lower unwind release force can maintain desiredcontact between the carrier and dry paint film during unwinding andapplication to a substrate surface; but if the carrier release force istoo high, there may be difficulties in producing a proper release of therelease liner from the dry paint layer after the PSA side of thelaminate has been affixed to the substrate surface. If the carrierrelease force is too high, the user may experience difficulty ininitially peeling the liner from the paint film; or removing the releaseliner may overcome the bond between the dry paint layer and thesubstrate and result in peeling the dry paint layer from the surface.

Therefore, another objective of the invention is to produce adifferential release system in which the carrier release force is higherthan the unwind release force over a broad range of release rates, butthe carrier release force level is maintained below a certain maximumforce level. In one embodiment, a preferred dry paint layer comprises atransparent outer clear coat layer as described in Examples 7 and 9, inwhich the outer layer comprises a solvent-cast acrylic resinousmaterial. This top coat material provides benefits of abrasion and stainresistance and repaintability in the finished film in addition to auseful carrier release force level when the matte release liner ispeeled from the outer layer. The composition of the matte release coatin this embodiment comprises the alkyd/vinyl/melamine resinouscomposition of Examples 7 or 9, and the composition of the PSA comprisesthe adhesive formulation of Examples 7 or 9. In this embodiment, thecarrier release force when peeled from the acrylic-based paint layer ismaintained within a range of about 45 to about 65 grams per 2 inches.Corresponding unwind release force is maintained within a range of about20 to about 40 grams per 2 inches, over a range of liner release ratesfrom about 12 to at least about 60 inches per minute. It has beenobserved that the lower carrier release force level associated with theacrylic-based outer clear coat layer, i.e., below about 65 grams per 2inches, provides sufficiently low carrier release properties to enableusers to easily remove the release liner over a wide range of useconditions and carrier release rates.

By lowering the unwind release force response, the carrier release forcethen can be lowered to a more desirable level as mentioned previously.The PSA used in the present invention is preferably an internallycross-linked pressure-sensitive adhesive which lowers peel and tacklevels. In one embodiment, the internally cross-linked acrylate-basedcopolymer emulsion PSA of Example 9, for instance, produces unwindrelease levels that are sufficiently low to allow use of matte releasecoatings that produce carrier release responses at the more desirablelower levels as described previously. Use of a non-crosslinked (orlightly crosslinked) pressure-sensitive adhesive, which is softer, canhave undesirable edge ooze characteristics during use; but in addition,it can produce higher peel and tack levels that undesirably increase theunwind release force in a direction toward the carrier release force.

The matte release coat composition also can control the carrier releaseforce level. In the matte release coat formulation of Examples 7 and 9,the melamine crosslinking agent can be used to control the carrierrelease force level. The content of the alkyd resin and the lowermolecular weight vinyl resin also can be controlled to lower releaseforce. A useful combination of these components can produce desired roomtemperature adhesion to the release liner and release force responsewhen peeling the release liner from the dry paint layer surface. Therelease coat composition also controls uniformity of and gloss level ofthe transferred matte surface.

As mentioned, the tack or peel level of the PSA also is controlled withrespect to the surface to which the laminate is affixed. That is, thePSA in its dry form must have a low unwind release force from thesilicone-coated release liner but also must have a sufficient level oftack to properly adhere to a substrate surface as well as providingsufficient repositionability.

A pressure sensitive adhesive useful for this invention is characterizedby relatively low tack and peel force levels and relatively low roomtemperature flow properties. Such adhesives, if they are too soft, canundesirably increase unwind force and can adversely affect repositioningof the paint film. Acrylic emulsion PSAs are particularly useful whensuch PSAs have a level of crosslinking that produces an adhesivematerial with a relatively high cohesive strength that yields adesirable combination of low tack, peel and flow properties. Examples ofuseful PSAs in which the level of crosslinking can be appropriatelyadjusted include acrylic emulsion PSAs such as pure polymer (butylacrylate or 2-ethyl hexyl acrylate or 2-ethyl hexyl acrylate/butylacrylate) PSAs or similar pigmented polymer and copolymer materials.

A particularly useful PSA for this invention is an internallycross-linked acrylic emulsion PSA such as a non-tackified cross-linkedcopolymer emulsion of butyl acrylate and 2-ethyl hexyl acrylate. Thisparticular adhesive contains a crosslinking agent which controls thelevel of crosslinking and produces a desirable combination of low tack,peel and flow and relatively high cohesive strength at a useful low coatweight. This adhesive is available from Avery Dennison Corporation asproduct no. S-3506, or in its pigmented form as product no. S-3526.

Other multi-functional acrylic-based polymer and copolymer materials canbe used to produce similar adhesive properties in their cross-linkedform. In addition, other suitable pressure-sensitive adhesives for thisinvention can comprise high molecular weight acrylic emulsion adhesives.Such high molecular weight adhesives can behave in a manner similar tothe cross-linked adhesives in producing low tack, peel and flowcharacteristics at sufficiently high cohesive strength. Exteriorcrosslinking agents also can be used to provide the desired level ofcrosslinking in such pressure sensitive adhesives materials.

Another useful adhesive is a high molecular weight cross-linked acrylicemulsion adhesive (butyl acrylate/2-ethyl hexyl acrylate) available fromAvery Dennison as product no. S-3000.

As mentioned previously, the PSA useful for this invention can becharacterized, in part, as an adhesive that produces an unwind releaseforce which is lower than the carrier release force, when releasing fromcontact with a silicone-coated release liner. The PSA also can becharacterized, in part, by its level of adhesion to a substrate such asflat paint, glossy paint, primed drywall or stainless steel, forexample. In one embodiment, the PSA formulation can be controlled toproduce a low level of tack characterized by a looptack value within therange of about 0.8 to about 2.4 lbs/in, in which the adhesive ismeasured for adhesion to stainless steel and laminated to a 2 mil PETfacestock, at a standard coat weight of 15 gsm.

In another embodiment, the PSA formulation can be controlled to producea low level of 90° peel force adhesion, characterized by 15 minute peeladhesion to stainless steel in the range of 0.80 to 1.5 lbs/in for 2 milPET; or 15 minute peel adhesion to flat painted surfaces of 0.05 to 0.30lbs/in, or 15 minute peel adhesion to glossy painted surfaces of 0.20 to0.40 lbs/in in which the adhesive is laminated to the dry paint transferfilm with the release liner carrier.

In another embodiment, the PSA can be adjusted to produce a low peelforce characterized by 90° peel adhesion values at 24 hours as follows:dry wall—0.30 to 0.50 lbs/in; flat paint—0.40 to 0.65 lbs/in; and glossypaint—0.60 to 0.90 lbs/in.

The PSA also can be characterized by its desired low flow properties atroom temperature. Such characteristics can be measured by its WPI(plasticity) value which in one embodiment has a WPI value from about3.2 to about 3.8 mm.

The desired PSA also has a sufficient level of cohesive strength thatenables the adhesive to permanently bond the paint film to the wall inthe absence of a high level of tack. The level of crosslinking caneffect such a cohesive strength, and in one embodiment, the cohesivestrength is measured by a shear value of greater than 1,000 minutes (500g ¼ sq. in., 20 minute dwell, 14-16′ gsm coat weight direct coated on 2mil PET dried at 120° C. for 5 minutes).

EXAMPLES 1 AND 2

A polyethylene terephthalate (PET) release liner is coated on one sidewith a silicone release coating corresponding to the adhesive releasecoating layer. The thickness of the release coated liner is 0.92 mil,also known as Mitsubishi 92 gauge SLK.

A matte release coat is applied to the other side of the release linerusing gravure at a coat weight of 6.5-7.75 gsm. The formulation for thematte release coat is as follows: 26 parts by weight methylisobutylketone, 6 parts by weight isopropanol, 34.8 parts by weight Lankyd13-1425 (a product supplied by Akzo Resins identified as an acrylicmodified alkyd), 2.6 parts by weight Elvacite 2042 (a product suppliedby Lucite International identified as a polyethyl methacrylate polymer),30 parts by weight Microtalc MP 15-38 (a product supplied by BarrettsMinerals identified as a talc extender pigment), 2.5 parts by weightCycat 4040 (a product supplied by Cytec identified as paratoluenesulfonic acid), and 8.7 parts by weight Cymel 303 (a product supplied byCytec identified as a melamine resin). The matte release coat is driedusing forced hot air at a temperature of 149° C. which crosslinks theresin and bonds the matte silicone coat to the polyester carrier. Thetalc particles project from the surface of the dried matte release coatto form a microroughened surface.

A transparent clear coat layer is applied to the matte release coatusing gravure at a coat weight of 2.7-2.9 gsm and dried using forced hotair at a temperature of 120° C. The formulation for the clear coat layeris as follows: 46.7% by weight methyl ethyl ketone, 31.3% by weighttoluene, 11% by weight VYNS (a product of Union Carbide identified as avinyl chloride/vinyl acetate copolymer containing 5-20% by weight vinylacetate), and 11% by weight Vitel 2200B (a product of Bostic identifiedas a polyester copolymer).

The following paint compositions are used to form a dry paint layer onthe clear coat layer, one for Example 1 and the other for Example 2. Thedry paint layer of Example 1 has a deep brown tone, while the dry paintlayer of Example 2 has an orange pastel tone. In the following table,all numerical values are in parts by weight. Component Example 1 Example2 Methylethyl ketone 66.7 66.7 Toluene 33.3 33.3 VYHH (product of UnionCarbide 50.05 30.55 identified as a vinyl chloride/vinyl acetatecopolymer) Edenol 9790 (a product of Cognis 24.65 15.05 identified as apolyester plasticizer) Yellow pigment 42 (iron oxide) 17.8 2.3 Orangepigment 36 (monoazo 2.5 0.38 benzimidazoline) Black 7 (carbon black) 0.10.02 White 6 (titanium dioxide) 4.9 51.7

The pigment-to-binder volume ratio for Example 1 is 10%, and for Example2 the ratio is 27%. The above paint formulations are applied to theclear coat layer using a reverse roll coater and are dried at atemperature of 135° C. to drive off the solvents. The dry film thicknessof each of the dry paint layers is 0.7 mil.

A pigmented pressure sensitive adhesive is then applied to the dry paintlayer at a coat weight of 14-20 gsm using transfer lamination to providean adhesive layer corresponding to pressure sensitive adhesive layer120. The adhesive is an ethyl hexyl acrylate based PSA available fromAvery Dennison Corporation under product no. S-692N and the formulationfor the pressure sensitive adhesive is as follows: 70-90% by weight2-ethyl hexyl acrylate, 1-10% by weight acrylic acid, 10-20% by weightmethyl acrylate, 3.7% UCD 1106E (a product of Rohm and Haas identifiedas a titanium dioxide dispersion concentrate), and 0.3% by weight of UCD1507E (a product of Rohm and Haas identified as a carbon blackdispersion concentrate).

EXAMPLE 3

The procedure used for Examples 1 and 2 is repeated except that thefollowing liquid paint composition is used to form the dry paint layer.In the following table, all numerical values are in parts by weight.Component Parts Methylethyl ketone 29.6 Toluene 19.5 Vitel 2200 B 11.6Vitel 2650 (product of Bostic identified 11.5 as a polyester copolymer)R-900 (product of DuPont identified as 27.5 titanium dioxide) 955-39230(product of Gibraltar Chemical 0.2 Works identified as shading black)99-34520 (product of Gibraltar Chemical 0.1 Works identified as phthaloblue GS) 955-37470 (product of Gibraltar Chemical tint Works identifiedas carbazole violet)

The foregoing paint composition has a light blue color. The dry filmthickness of the dry paint film layer is 0.6-0.8 mil.

EXAMPLE 4

A PET release liner is coated on one side with a silicone releasecoating corresponding to the adhesive release coat layer. The thicknessof the release coated liner is 0.92 mil.

A matte release coat layer is applied to the other side of the releaseliner using gravure at a coat weight of 4.4-4.6 gsm. The formulation forthe matte release coat is as follows: 50.54 parts by weightmethylisobutyl ketone, 7.84 parts by weight isopropanol, 8.93 parts byweight Lankyd 13-1425, 10.68 parts by weight VAGH (product of UnionCarbide identified as hydroxy modified polyvinyl chloride/polyvinylacetate copolymer), 22 parts by weight Microtalc MP 15-38, 2 parts byweight Cycat 4040, and 6.8 parts by weight Cymel 303. The matte releasecoat is dried using forced hot air at a temperature of 149° C.

A first coat of a transparent outer clear coat layer is applied to thematte release coat using gravure at a coat weight of 1.3-2 gsm and driedusing forced hot air at a temperature of 120° C. The dry film thicknessis 0.05-0.1 mil. The formulation for this first clear coat layer is asfollows: 41.5% by weight methyl ethyl ketone, 41.5% by weight methylisobutyl ketone, and 17% by weight Elvacite 2042 (a product of LuciteInternational identified as a polymethyl methacrylate).

A second coat of a clear coat layer is applied over the firsttransparent layer using gravure at a coat weight of 1.0-1.5 gsm anddried using forced hot air at a temperature of 120° C. The dry filmthickness is 0.03-0.1 mil. The formulation for this second transparentfilm layer coat is as follows: 41.5% by weight methyl ethyl ketone,41.5% by weight methyl isobutyl ketone, and 17% by weight VYHH (aproduct of Union Carbide identified as a vinyl chloride/vinyl acetatecopolymer containing 5-20% by weight vinyl acetate).

A decorative print layer is printed over the second transparent clearcoat layer at a coat weight of 3.0-3.2 gsm and dried in hot air at atemperature of 120° C. The paint composition for this decorative printlayer has the following formulation (all numerical values are in partsby weight): Component Parts Methylethyl ketone 42.6 Methyl isobutylketone 38.7 VYHH 15.86 DP 80110 (product of Gibraltar Chemical 2.1 Worksidentified as containing methylethyl ketone, toluene, carbon black andacrylic polymer) DP 36640 (product of Gibraltar Chemical 0.22 Worksidentified as containing methyl ethyl ketone, toluene, quinacridone red,and acrylic polymer) I8977 (product of Gibraltar Chemical 0.10 Worksidentified as containing methyl ethyl ketone, toluene, R.S. PhthaloBlue, and acrylic polymer) I8980 (product of Gibraltar Chemical 0.38Works identified as containing methyl ethyl ketone, toluene,isoindolinone yellow and acrylic polymer)

An additional decorative print layer is printed over the previousdecorative print layer at a coat weight of 0.8 gsm and dried in hot airat a temperature of 120° C. The paint composition used for thisdecorative print layer has the following formulation (all numericalvalues are in parts by weight): Component Parts Methylethyl ketone 42.85Methyl isobutyl ketone 39.1 VYHH 16.0 DP 80110 1.71 DP 36640 0.18 189770.18

The following paint composition is coated over the two dried print coatlayers at a coat weight of 30-32 gsm and dried in hot air at atemperature of 120° C. to provide a dry paint. In the following table,all numerical values are in parts by weight. Component Parts Methylethyl ketone 34 Toluene 16.7 VYHH 18.3 Edenol 9790 9 AVI-0301-3 Orange(product of Gibraltar 8.9 Chemical Works identified as containing methylethyl ketone, toluene, diarylide orange, VYHH and Edenol 9790)AVI-0301-5 Magenta (product of Gibraltar 5.3 Chemical Works identifiedas containing methyl ethyl ketone, toluene, Metal Azo Red, VYHH andEdenol 9790) AVI-0301-6 Iron Red (product of Gibraltar 3.7 ChemicalWorks identified as containing methyl ethyl ketone, toluene, Iron OxideRed, VYHH and Edenol 9790) AVI-0301-1 TiO₂ White (product of Gibraltar3.52 Chemical Works identified as containing methyl ethyl ketone,toluene, titanium dioxide, VYHH and Edenol 9790) AVI-0301-2 Carbon Black(product of 0.03 Gibraltar Chemical Works identified as containingmethyl ethyl ketone, toluene, carbon black, VYHH and Edenol 9790)

A pigmented pressure sensitive adhesive is then applied over the drypaint layer at a coat weight of 17 gsm using transfer lamination toprovide an adhesive layer corresponding to pressure sensitive adhesivelayer. The formulation for the pressure sensitive adhesive is asfollows: 96% by weight of a non-tackified acrylic emulsion containing across-linked copolymer of butyl acrylate and 2-ethyl hexyl acrylate,3.7% by weight UCD 1106E, and 0.3% by weight UCD 1507E.

EXAMPLE 5

A PET release liner is coated on one side with a silicone releasecoating. The thickness of the release coated liner is 0.92 mil.

A matte release coat is applied to the other side of the release linerusing gravure at a coat weight of 4.4-4.6 gsm. The matte release coat isdried using forced hot air at a temperature of 149° C. The formulationfor the matte release coat is as follows (all numerical values are inparts by weight): Component Parts Methyl isobutyl ketone 52.54 Elvacite4402 (product of Lucite 20.98 International identified as hydroxy ethylmethacrylate modified acrylic resin) VYNS 1.35 Microtalc 15-38 22.85 Byk451 (product supplied by Byk 2.2 Chemie identified as blocked acidcatalyst) Cymel 303 6.38

A transparent clear coat layer is applied to the matte release coatusing a reverse roll coater at a coat weight of 13 gsm and dried usingforced hot air at a temperature of 120° C. The dry film thickness is 0.4mil. The formulation for the transparent clear coat layer is as follows(all numerical values are in parts by weight): Component Parts RucothaneCO-A-5002L (product 62.5 of Ruco Chemical identified as polyesterurethane) Toluene 18.75 Isopropanol 18.75

A decorative print layer is printed over the above indicated transparentfilm layer at a coat weight of 1 gsm and dried in hot air at atemperature of 120° C. The paint composition used for this decorativelayer has the following formulation (all numerical values are in partsby weight): Component Parts Methyl ethyl ketone 25.67 Methyl isobutylketone 22.0 VYHH 9.17 I8980 3.5 DP 37251 (product of Gibraltar Chemical0.99 Works identified as containing perylene red, methyl ethyl ketone,toluene and acrylic polymer) DP80110 1.0 DP39600 (product of GibraltarChemical 37.47 Works identified as containing TiO₂, methyl ethyl ketone,toluene and acrylic polymer) I8977 0.20

The following paint composition is coated over the decorative printlayer at a coat weight of 66 gsm and dried in hot air at a temperatureof 138° C. to form a dry paint layer. In the following table, allnumerical values are in parts by weight: Component Parts Methyl isobutylketone 24.11 Toluene 20.65 VYHH 11.54 R-900 38.4 Acryloid B-72 (productof Rohm and 3.86 Haas identified as an acrylic resin) I8980 2.6 DP372510.21 DP80110 0.40

A pressure sensitive adhesive is then applied over the dry paint layerat a coat weight of 15-20 gsm using transfer lamination to provide anadhesive layer. The pressure sensitive adhesive is a non-tackifiedacrylic emulsion. The formulation for the pressure sensitive adhesive isas follows: 70-90% by weight 2-ethyl hexyl acrylate, 1-10% by weightacrylic acid, and 10-20% by weight methyl acrylate.

EXAMPLE 6

A PET release liner is coated on one side with a silicone releasecoating. The thickness of the release coated liner is 0.92 mil.

A matte release coat is applied to the other side of the release linerusing gravure. The release coat is dried using forced hot air at atemperature of 148.9° C. The matte release coat is applied at a coatweight of 4.0-5.0 gsm. The formulation for the matte release coat is asfollows (all numerical values are in parts by weight): Component PartsMethyl isobutyl ketone 42.03 Isopropanol 8.51 Microtalc 15-38 23.87Cymel 303 7.36 Cycat 4040 1.8 VROH (product supplied by 16.43 UnionCarbide identified as a vinyl chloride/vinyl acetate copolymer with OHfunctionality)

A transparent clear coat layer is applied over the matte release coatusing a 2 mil byrd bar at a coat weight of 30 gsm and dried using hotair at a temperature of 126.7° C. The formulation for the transparentfilm layer is as follows (all numerical values are in parts by weight):Component Parts Water 7.98 N-methyl pyrrolidone 4.79 Texanol (product ofEastman 4.79 Chemicals identified as an ester alcohol) BYK 333 (productof Byk Chemie 0.4 identified as a wetting agent) Vycar 351 (product ofNoveon identified 79.81 as a polyvinyl chloride copolymer emulsion)Antifoam PD-218 (product of Magrabar 0.32 Chemical identified as anantifoam agent) Rheolate 350 (product of Ŕheox, Inc. 1.92 identified asa thickener)

The following paint composition is coated over the transparent clearcoat film at a coat weight of 96 gsm and dried in hot air at atemperature of 126.7° C. to form a dry paint film layer. In thefollowing table, all numerical values are in parts by weight: ComponentParts Water 18.28 Surfynol CT-324 (product of Air 0.98 Productsidentified as a surfactant) R-900 32.88 Vycar 460X45 (product of Noveonidentified 34.72 as a vinyl chloride/acrylic copolymer) Vycar 460X46(product of Noveon identified 11.57 as a vinyl chloride/acryliccopolymer) Antifoam PD-218 0.19 Byk 333 0.23 Rheolate 350 1.2

A pressure sensitive adhesive layer is then applied over the dry paintlayer at a coat weight of 17 gsm using transfer lamination to provide anadhesive layer corresponding to pressure sensitive adhesive layer. Theformulation for the pressure sensitive adhesive is as follows: 96% byweight of a non-tackified emulsion containing a cross-linked copolymerof butyl acrylate and 2-ethyl hexyl acrylate, 3.7% by weight UCD 1106E,and 0.3% by weight UCD 1507E.

EXAMPLE 7

A PET release liner is coated on one side with a silicone release coatlayer. The thickness of the release coated liner is 0.92 mil.

A matte release coat is applied to the other side of the release linerusing gravure at a coat weight of 4.4-4.6 gsm. The formulation for thematte release coat is as follows: 50.54 parts by weight methyl isobutylketone, 7.84 parts by weight isopropanol, 8.93 parts by weight Lankyd13-1425, 10.68 parts by weight VAGH (product of Union Carbide identifiedas hydroxy modified polyvinyl chloride/polyvinyl acetate copolymer), 22parts by weight Microtalc MP 15-38, 2 parts by weight Cycat 4040, and6.8 parts by weight Cymel 303. The matte release coat is dried usingforced hot air at a temperature of 149° C.

A transparent clear coat layer is applied to the matte release coatusing gravure at a coat weight of 12-16 gsm and dried using forced hotair at a temperature of 165° C. The dry film thickness is 0.35-0.5 mil.The formulation for this transparent film layer is as follows (allnumerical values are in parts by weight): Component Parts Cyclohexanone69.3 Elvacite 2042 10.5 Solsperse 17000 (product of Avecia 0.1identified as a wetting agent) Tinuvin 234 (product of Ciba identified0.6 as a light stabilizer) Kynar 301F (product of Atofina 27.0identified as a polyvinyl fluoride homopolymer) N-methyl-2-pyrrolidone2.5

A decorative print layer is printed over the transparent coating layerat a coat weight of 0.3-1.2 gsm and dried in hot air at a temperature of105° C. The paint composition used for this decorative layer has thefollowing formulation (all numerical values are in parts by weight):Component Parts Methylethyl ketone 36.0 Methyl propyl ketone 35.1 Kynar7201 (SL) (product of Atofina 10.2 identified as a polyvinyl fluoridecopolymer) Elvacite 2010 (product of Lucite 3.4 International identifiedas a polymethyl methacrylate) Tinuvin 234 0.27 DP35740 (product ofGibraltar 0.10 Chemical Works identified as a buff mixed metal oxidepigment concentrate) DP35820 (product of Gibraltar 11.7 Chemical Worksidentified as a brown mixed metal oxide pigment concentrate) DP39040(product of Gibraltar 3.3 Chemical Works identified as a black mixedmetal oxide pigment concentrate)

An additional decorative print layer is printed over the previousprinted decorative layer at a coat weight of 0.3-1.2 gsm and dried inhot air at a temperature of 105° C. The paint composition used for thisdecorative print layer has the following formulation (all numericalvalues are in parts by weight): Component Parts Methylethyl ketone 34.0Methyl propyl ketone 33.0 Kynar 7201 (SL) 9.6 Elvacite 2010 3.2 Tinuvin234 0.25 DP35740 14.4 DP35820 5.0 DP39040 3.2

The following paint composition is coated over the decorative printlayers at a coat weight of 6-10 gsm and dried in hot air at atemperature of 105° C. to provide a dry paint film layer correspondingto dry paint film layer 110. In the following table, all numericalvalues are in parts by weight. Component Parts Methyl ethyl ketone 27.6Methyl propyl ketone 26.3 Kynar 7201 (SL) 7.4 Elvacite 2010 2.5 Tinuvin234 0.2 DP35740 4.1 DP35820 7.8 DP39040 0.6 DP39600 (product ofGibraltar 23.6 Chemical Works identified as a white titanium dioxidepigment concentrate)

A pigmented pressure sensitive adhesive is then applied over the drypaint layer at a coat weight of 17 gsm using transfer lamination toprovide an adhesive layer corresponding to pressure sensitive adhesivelayer 120. The formulation for the pressure sensitive adhesive is asfollows: 96% by weight of a non-tackified acrylic emulsion containing across-linked copolymer of butyl acrylate and ethyl hexyl acrylate, 3.7%by weight UCD 1106E, and 0.3% by weight UCD 1507E.

EXAMPLE 8

A PET release liner is coated on one side with a silicone releasecoating corresponding to the adhesive release coat layer. The thicknessof the release coated liner is 0.92 mil.

A matte release coat is applied to the other side of the release linerusing gravure at a coat weight of 4.4-4.6 gsm. The formulation for thematte release coat is as follows: 50.54 parts by weight methylisobutylketone, 7.84 parts by weight isopropanol, 8.93 parts by weight Lankyd13-1425, 10.68 parts by weight VAGH (product of Union Carbide identifiedas hydroxy modified polyvinyl chloride/polyvinyl acetate copolymer), 22parts by weight Microtalc MP 15-38, 2 parts by weight Cycat 4040, and6.8 parts by weight Cymel 303. The matte release coat is dried usingforced hot air at a temperature of 149° C.

A decorative print layer is printed over the matte release coat at acoat weight of 0.3-1.2 gsm and dried in hot air at a temperature of 105°C. The paint composition used for this decorative layer has thefollowing formulation (all numerical values are in parts by weight):Component Parts Methylethyl ketone 36.0 Methyl propyl ketone 35.1 Kynar7201 (SL) (product of Atofina 10.2 identified as a polyvinyl fluoridecopolymer) Elvacite 2010 (product of Lucite 3.4 International identifiedas a polymethyl methacrylate) Tinuvin 234 0.27 DP35740 (product ofGibraltar 0.10 Chemical Works identified as a buff mixed metal oxidepigment concentrate) DP35820 (product of Gibraltar 11.7 Chemical Worksidentified as a brown mixed metal oxide pigment concentrate) DP39040(product of Gibraltar 3.3 Chemical Works identified as a black mixedmetal oxide pigment concentrate)

An additional decorative print layer is printed over the previousprinted decorative layer at a coat weight of 0.3-1.2 gsm and dried inhot air at a temperature of 105° C. The paint composition used for thisdecorative print layer has the following formulation (all numericalvalues are in parts by weight): Component Parts Methylethyl ketone 34.0Methyl propyl ketone 33.0 Kynar 7201 (SL) 9.6 Elvacite 2010 3.2 Tinuvin234 0.25 DP35740 14.4 DP35820 5.0

The following paint composition is coated using rotogravure over thedecorative print layers at a coat weight of 5-16 gsm and dried in hotair at a temperature of 105° C. to form a dry paint layer. In thefollowing table, all numerical values are in parts by weight. ComponentParts Toluene 19.0 Methyl ethyl ketone 23.6 VYHH 5.8 Edenol 9790 2.9DV39600 (product of Gibraltar 48.6 Chemical identified as iron oxide redpigment dispersion) DV39420 (product of Gibraltar 0.07 Chemicalidentified as carbon black pigment dispersion) DV36500 (product ofGibraltar 0.03 Chemical identified as Pigment Red 178 pigmentdispersion) DV34130 (product of Gibraltar 0.10 Chemical identified asPhtalo Blue RS pigment dispersion)

The following coating composition is coated over the dry paint layerusing roll coating at a coat weight of 20-30 gsm and dried in hot air ata temperature of 105° C. to form a support or reinforcing layer. In thefollowing table, all numerical values are in parts by weight: ComponentParts Toluene 14.1 Methyl ethyl ketone 21.1 VYHH 13.2 Edenol 9790 6.6DV39600 44.96 DV39420 0.04

A pigmented pressure sensitive adhesive is then applied over the coatedlayer corresponding to support layer 180 at a coat weight of 17 gsmusing transfer lamination to provide an adhesive layer corresponding topressure sensitive adhesive layer 120. The formulation for the pressuresensitive adhesive is as follows: 96% by weight of a non-tackifiedacrylic emulsion containing a cross-linked copolymer of butyl acrylateand 2-ethyl hexyl acrylate, 3.7% by weight UCD 1106E, and 0.3% by weightUCD 1507E.

EXAMPLE 9

FIG. 10 illustrates one embodiment of the invention in which adecorative laminate 89 includes a dry paint layer coated in sequenceonto a release liner 30 which includes a matte release coat 32 on oneside and an adhesive release layer 34 on the side opposite the dry paintlayer. The dry paint layer comprises an outer clear coat layer 44, oneor more decorative print coats 48, and a color layer 22. A barrier layer60 is bonded to the color layer and a tie coat 90 is bonded to thebarrier coat and the PSA layer 28.

A PET liner is coated on one side with a silicone release coatingcorresponding to the adhesive release coat layer. The thickness of thesilicone coated liner is 0.92 mil and comprises Mitsubishi 92 gauge SLK.

The matte release coat is applied to the other side of the release linerusing gravure at a coat weight of 4.5 to 5.5 gsm. The formulation forthe matte release coat is as follows (with all numerical values in partsby weight): Component Parts Methyl isobutyl ketone (MiBK) 53.47Isopropanol 6.49 Lankyd 13-1245 (product of Akzo 7.21 Chemical,identified as an acrylic modified alkyd) VAGH 8.72 EFKA 5055 (acarboxylic acid ester 1.10 dispersing agent) Microtalc MP 15-38 23.02Cymel 303 (Cytec melamine resin) 7.45 Byk 451 (Byk Chemie blocked acidcatalyst) 3.50

In preparing the release coat material the base materials (VAGH, alkydand talc) are compounded in a 100 part formula. The Cymel 303 and Byk451 are later blended and after the materials are delivered to thecoater the two solutions are blended together. The matte release coat isdried using forced air at a temperature of 149° C.

The matte release coat comprises as its crosslinking resin the melamine(hexamethoxy methyl) resin Cymel 303. The hydroxyl modified polyvinylchloride/polyvinyl acetate copolymers (VAGH) comprise the primaryfunctional resin and the acrylic modified alkyd comprises a secondaryfunctional resin. The primary crosslinking resin controls crosslinkingand bonds to the polyester carrier film. The secondary functional resinmodifies release of the dry paint layer (top coat) from the matterelease coat. The blocked acid catalyst accelerates the crosslinkingprocess and the filler particles, talc, control the degree ofmicroroughness of the dry matte release coat.

A transparent clear coat layer is applied to the matte release coatusing gravure at a coat weight of 2.6 to 3.0 gsm and dried using forcedhot air at a temperature of 165° C. The dry film thickness is 0.09-0.10mil. The clear coat consists essentially of a thermoplastic acrylicresinous material, preferably polymethyl methacrylate. The formulationfor the transparent top coat layer (with all numerical values in partsby weight) is as follows: Component Parts MEK 40 MiBK 41 Elvacite 204219

One or more decorative print coats having printing ink formulationssimilar to those described in previous examples are next printed overthe transparent top coat layer following procedures as describedpreviously.

The following paint coat composition comprises a plasticized vinyl-basedpigmented base coat having an epoxy stabilizer. The tie coat is coatedover the decorative print layers, using roll coating at a coat weight of33.0 to 36.0 gsm and dried in hot air at a temperature of 105° C. toform a color coat layer. The dry film thickness is 0.65 to 0.73 mil. Inthe following table all numerical values are in parts by weight:Component Parts NiPar 820 (product of Angus Chemical 15.98 identified asa blend of 80% nitro propane and 20% nitro ethane) Xylene 23.95Cyclohexanone 7.71 VYHH 12.76 Edenol 9790 6.38 Stanclere T-883 (productof Adchross 0.06 Chemical identified as a tin heat stabilizer) EPON 828(epoxy resin product of Shell) 0.26 DV 39600 (Gibraltar TiO₂ white 32.12pigment dispersion) DV 396420 (Gibraltar carbon black 0.23 pigmentdispersion) DV 36500 (Gibraltar red pigment 0.16 dispersion) DV 34130(Gibraltar phthalo blue 0.39 pigment dispersion)

The following barrier coat layer is coated over the dried color coatlayer at a coat weight of 1.5 to 2.0 gsm. All numerical values are inparts by weight: Component Parts Adcoat 61WG178 (a product of Rohm 45and Haas identified as acrylic polymer) Isopropanol 52 Cymel 303 (Cytecmelamine resin) 2.4 Cycat 4040 (Cytec paratoluene 0.2 sulfonic acid)

The barrier layer comprises a cross-linked acrylic resinous materialwhich is applied by gravure and dried, using forced air at a temperatureof 149° C. The dry film thickness of the barrier layer is 0.05 to 0.07mil.

As mentioned previously, the barrier layer provides a means forinhibiting or preventing migration of discoloration-causing pigmentsinto the color-producing layers of the laminate.

The following tie coat is coated over the dried barrier layer. Allnumerical values are in parts by weight: Component Parts MEK 25.24 MiBK25.59 VYHH 8.98 Edenol 9790 plasticizer 4.49 Stanclere T-883 0.04 EPON828 0.18 DV 39600 35.03 DV 39420 0.45

The tie coat is coated at a coat weight of 2.8 to 3.3 gsm and with a dryfilm thickness from about 0.05 to 0.06 mil. The tie coat enhancesadhesion between the barrier layer and the pressure sensitive adhesivelayer. The tie coat is a variation of the color coat. In the presentsystem, the barrier layer adheres to the color coat and the PSA adhereswell to a similar color coat; so the tie coat is selected for itsability to provide good adhesion between the color coat and the PSA. Thepigment component of the tie coat hardens the binder to a useful level.

The dry film thickness of the decorative laminate of this Example iswithin a preferred range of 1.30 to 1.60 mil. In the described example,the dry film thickness of the combined top coat, color coat, barriercoat, tie coat and PSA is from 1.35 to 1.51 mil.

A pigmented pressure sensitive adhesive layer is then applied to acarrier at a coat weight of 13 to 16 gsm. The dry film thickness of thePSA is from about 0.45 to 0.55 mil. The PSA is then applied to the tiecoat by transfer lamination. The PSA is available from Avery DennisonCorporation under product no. S-3526 and the formulation for the PSA isas follows (with numerical values in parts by weight): Component PartsS-3506 (product of Avery Dennison, 96.0 Performance Polymers, identifiedas a cross-linked copolymer emulsion of butyl acrylate and 2-ethyl hexylacrylate) UCD 110GE (white TiO₂ pigment 3.7 dispersion from Rohm andHaas) UCD 1507E (carbon black pigment 0.3 dispersion from Rohm and Haas)

EXAMPLE 10

Gloss measurements taken on the Byk-Mallinckrodt gloss meter for variouspaint films as described herein produced the following gloss readings:

(1) Release coat—Elvacite 2899/VYNS at a ratio of 14.5:1, having astandard range of microtalc at 1.0 to 1.1:1 talc to polymer with Cymel303

Top coat—none

Color coat—Rohm and Haas Acryloid B72/VYHH at a ratio of 1:3

-   -   Gloss at 60°—3.4    -   Gloss at 85°—8.8

(2) Release coat—Elvacite 2899/VYNS at a ratio of 14.5:1, having astandard range of microtalc at 1.0 to 1.1:1 talc to polymer with Cymel303

Top coat—Rucothane CO A 5002L urethane polymer

Color coat—Rohm and Haas B72/VYHH at a ratio of 1:3

-   -   Gloss at 60°—4.9    -   Gloss at 85°—8.5

(3) Film having faux leather finish:

Release coat—Acrylic modified alkyd with Cymel 303 and standard range ofmicrotalc at 1.0 to 1.1:1 talc to polymer.

Top coat—Elvacite 2042 and VYHH/Vitel 220B at 1:1 ratio.

Gloss at 60°—2.2

Gloss at 85°—32.4

(4) Films having release coats and transparent top coat layers preparedaccording to Examples 7 and 9 produced gloss readings within a rangefrom about 26 to about 30 at 85°.

EXAMPLE 11

To measure the “force differential” in terms of carrier release forceversus unwind release force, samples were produced in two-inch-wide by12-inch long strips to simulate unwinding of a roll of the decorativefilm. A construction under test comprised the FIG. 3 embodiment having atransparent top coat, pigmented color layer, a PSA layer with the PSAside of the film exposed, and a release liner comprising a PET filmhaving a matte release coat in contact with the top coat and an exposedsilicone release coat on the opposite side of the release liner. Inother tests, the construction was similar to that shown in FIG. 10 inwhich the same construction included the barrier layer and the tie coatlayer.

One comparative test used test samples in which the compositions of thetransparent top coat, the color coat and the PSA layer were generally asdescribed in Examples 7 and 9, which included the Avery Dennison S-3506PSA layer (an unpigmented form of Avery S-3526 adhesive). In other testsamples, color coat and top coat formulations similar to Example 1 wereused, in combination with the Avery S-3506 PSA layer. In further testsamples, a construction involved the top coat and color coatformulations of Example 1 along with a different Avery Dennison PSAidentified as S-692N adhesive.

The tests involved peeling the matte release layer away from the drypaint layer and peeling the silicone side of the release liner away fromthe PSA part of the sample. The tests were conducted at roomtemperature. In one test, separate adhesive tapes were attached to thesides of the test samples to test the peel force at each interface witheach tape extending in opposite directions, each at a 90° angle to thesample. The tests were performed on a movable sled having adjustablepeel rates which, in one embodiment, were varied in increments fromspeeds as low as 12 inches per minute up to 1200 inches per minute. Peelforces were measured at progressive speed intervals and plotted oncomparative force-versus-peel rate profiles.

The test results showed that carrier release force is reasonably uniformacross a broad range of release rates, whereas unwind release forcestend to stay below the carrier release force at low speeds, but theyapproach and ultimately exceed the carrier force at higher speeds. Eachprofile generated by the tests was characterized by a cross-over releaserate at which the unwind release force reaches and exceeds the carrierrelease force. Generally speaking, the self wound rolls that producedthe best unwind response maintained a carrier release force in excess ofthe unwind release force at rates up to about 100 inches per minute. Thetest results showed that unwind force for the S-692N PSA approachedcarrier release force more rapidly than and exceeded it at a much lowerpropagation rate than the S-3506 PSA, which had superior unwindperformance compared to the S-692N PSA. Such superior unwind performancewas characterized by self-wound rolls of film containing the S-3506adhesive being unwound without premature release of the release linerfrom the dry paint layer; whereas rolls of film containing the S-692NPSA experienced unreliable release response.

It was also observed that the S-3506 PSA exhibited lower tack levels andhad less cold flow than the S-692N PSA. This was attributed to theS-3506 PSA having an internally cross-linked structure which producedthe lower tack levels and lower cold flow than the S-692N PSA which wasnot internally cross-linked and had higher tack levels, as well ashigher cold flow. This difference in PSA properties caused thenon-cross-linked PSA to stick more to the silicone side of the releaseliner and raised the unwind release force to levels that were too highand produced unreliable unwind response compared to the cross-linked PSAwhich produced more desirable (lower) unwind release force levels.

EXAMPLE 12

Test panels containing barrier coats were prepared and tested for colorshift. The test panels included a blue color layer similar to the colorlayer of Example 9 and a cross linked acrylic PSA layer, Avery's S-3506,similar to the PSA used in Example 9. The test films were applied to ayellow (Hansa Yellow 10G) painted surface and subjected to acceleratedaging. The test films were measured for discoloration (color shift)caused by migration of azo-type color constituents that passed from thepainted surface through the PSA layer to the color layer of the testsample. The test panels were prepared by using a dry paint color layercontaining a plasticized vinyl-based paint layer containing a dispersedblue pigment. The S-3506 PSA was applied to the color layer. A mediumyellow painted substrate was prepared using Behr 1300 deep base (5ounces medium yellow per gallon base) applied at 7.5 mils wet coating to3 mil polyester. The paint coat was allowed to dry for three hoursminimum at room temperature then force air dried for five minutes at250° F. The C.I.E. test procedures were used to measure Δ b* colorchange on the test panel at 60° C.

The following table shows six separate barrier coatings which wereevaluated for color shift using these test procedures. Test sample 1 wasa cross-linked low molecular weight acrylic barrier coat; test samples 2and 3 were thermoplastic low molecular weight acrylic barrier coatscontaining filler or additive materials for reducing color transmission;test samples 4 and 5 were thermoplastic low-molecular weight acrylicbarrier layers that included the filler or additive materials, but alsoincluded PVP as an adhesion promoter; and test sample 6 was a highmolecular weight thermoplastic acrylic barrier coat in the absence ofany additive, filler or adhesion promoter. The materials contained ineach test sample are shown in parts by weight. Barrier Coat Test SamplesMaterials #1 #2 #3 #4 #5 #6 Adcoat 61WG178 45.0 54.2 61.5 46.5 44.7acrylic Degussa Alum. Ox. 2.5 0.9 2.1 0.7 Halox Xtain A 2.5 0.9 2.1 0.7IPOH 52.4 40.8 36.7 35.0 26.6 20.0 Cymel 303 2.4 Cycat 4040 0.2 PVP K8014.3 27.3 Toluene 70.7 Elvacite 2041 9.3 acrylic

The following test results for test samples #1 through #6 show colorshift data for PSAs applied by both direct coating and bytransfer-lamination. Test Samples Materials #1 #2 #3 #4 #5 #6 Coatweight (gsm) 1.6 4.9 4.7 2.6 2.4 0.8 Direct adhesion good good good goodgood good Color change 60° C. 0.38/ 0.37/ 0.35/ 0.4/ (Δb*) 1170 hrs 552hrs 1002 hrs 1002 hrs Transfer- poor poor poor good good good laminationadhesion Color change 60° C. 0.47/ 0.97/ 0.61/ 0.89/ 0.39/ 0.38/ (Δ b*)162 hrs 239 hrs 330 hrs 201 hrs 376 hrs 552 hrs

A similar test was conducted using the cross-linked acrylic barrier coatof test sample #1 with the following tie coat (in parts by weight): TieCoat Material Parts MEK 25.22 MiBK 25.59 Dow VYHH 8.98 Plastolein 97904.49 Stanclere T-883 0.04 Dow EPON 828 0.18 DV39600 (Gibraltar White)35.30 DV29420 (Gibraltar Black 0.45 Disp.) MiBK 4.00

The product having the tie coat was tested as 60° C. for 401 hours.Samples for color shift measurement were taken throughout the roll. Anaverage of 0.24 Δb* color change resulted with a standard deviation of0.06. The tie coating was used in this test because the adhesive wasapplied by transfer-lamination, and the tie coat was needed to increasedadhesion between the barrier coat and the pressure sensitive adhesive.

Similar barrier polymer tests were conducted in which the C.I.E. Δb*color shift was measured for different test samples, and then the colorchange that would occur at 60° C. for 16 days was estimated. Coat wt.Final Proj. Barrier Polymer (gsm) Hrs. 16 days (1) Thermoplasticacrylic - R & H 2.5 400 1.82 61WG178 (2) Same as (1) 2.5 308 4.86 (3)Cross-linked acrylic - R & H 1.8 1337 0.25 61WG178/15 phr Cymel 303/1phr Cycat 4040 (4) Same as (3) 1.6 497 0.37 (5) Same as (3) 1.6 227 0.96(6) Cross-linked acrylic - R & H 1.8 1337 0.30 61WG178/10 phr Cymel303/1 phr Cycat 4040 (7) Cross-linked acrylic - R & H 1.6 487 0.2261WG178/15 phr Cymel 303/1 phr Cycat 4040/5 phr Ti02/9 phr AlO_(x) (8)Thermoplastic acrylic - R & H 2.0 427 0.12 61 WG 178/15 phr AlO_(x)/15phr Xtain.

General observations from these tests are that cross-linking of the lowmolecular weight acrylic barrier layer produces good color shiftimprovements into the acceptable range. Addition of titanium dioxide,aluminum oxide and similar metal compounds and oxides and salts furtherimprove the barrier properties of both thermoplastic and cross-linkedpolymeric barrier layers.

The present invention has been described with respect to multilayerlaminates used as a wall film for interior architectural applications,but the laminate also is useful in other applications as well. Thesewould include exterior architectural applications such as siding panelsand wall surfaces; outdoor decorative items and signs; interiorautomotive decorative and functional uses such as dashboards and panels;and exterior automotive uses including automotive body parts, trim partsand panels.

1. A multi-layer decorative laminate for applying a layer of color to asubstrate surface, the laminate comprising: a dry paint layer comprisinga color layer which includes a binder and a pigment, the dry) paintlayer having an upper surface and a lower surface, a pressure-sensitiveadhesive layer overlying the upper surface of the dry paint layer andadapted for adhering the laminate to a substrate surface at roomtemperature; a release liner overlying the lower surface of the drypaint layer, the release liner removable from the dry paint layer atroom temperature for exposing an outer surface of the dry paint layerwhen the pressure-sensitive adhesive layer adheres the laminate to thesubstrate surface under application of pressure and the release liner ispeeled away from the dry paint layer; and a barrier layer formed as athin, flexible barrier film disposed between the adhesive layer and thecolor layer, the barrier layer film positioned between the adhesivelayer and the color layer and made from a material so as to inhibitmigration of discoloration-causing pigments from a painted surface ofthe substrate through the adhesive layer to the color layer sufficientlyto essentially prevent noticeable color change caused by the migratingpigments from occurring in the color layer under room temperatureconditions, in which the barrier layer material is selected from thegroup consisting of an acrylic resinous material which has beencross-linked to an amount sufficient to reduce pigment transmission tothe color layer, a polymeric material containing an adhesion promoter, ahigh molecular weight acrylic resinous material having a molecularweight in excess of 250,000, or a polymeric material containing a fineparticulate dispersed barrier filler material that reduces pigmenttransmission to the color layer, the barrier filler material comprisinga metal oxide, a metal compound and/or a metal salt.
 2. The articleaccording to claim 1 in which the barrier layer is applied at a dry filmthickness in the range of about 0.05 to about 0.20 mil.
 3. The articleaccording to claim 1 in which the barrier layer has a glass transitiontemperature (Tg) greater than about 60° C.
 4. The article according toclaim 1 in which the barrier material has a dry film thickness of notmore than about 10% of the total thickness of the decorative laminate(exclusive of the release liner).
 5. The article according to claim 1 inwhich the laminate further includes a tie coat for enhancing adhesionbetween the cross-linked barrier layer and the pressure-sensitiveadhesive layer.
 6. The article according to claim 1 in which thepressure-sensitive adhesive comprises a cross-linked acrylic resinousmaterial.
 7. The article according to claim 1 in which thepressure-sensitive adhesive comprises an internally cross-linked acrylicemulsion.
 8. The article according to claim 1 in which the release linercomprising a matte release coat comprising a cross-linked resinousmaterial bonded to the release liner and having a micro-roughenedsurface that transfers a matte surface finish to the dry paint layer. 9.The article according to claim 8 in which the dry paint layer comprisesa pigmented color coat layer and a transparent outer clear coat layerbonded to the color coat and in contact with the release liner.
 10. Thearticle according to claim 9 in which the transparent outer clear coatlayer comprises an acrylic resinous material.
 11. The article accordingto claim 10 in which the pressure-sensitive adhesive layer comprises across-linked acrylic resinous material.
 12. The article according toclaim 1 in which the barrier layer material produces a color shift ofless than about 0.30 Δb* C.I.E. color scale shift units at 60° C.
 13. Amulti-layer decorative laminate for applying a layer of color to asubstrate surface, the laminate comprising: a dry paint layer comprisinga color layer which includes a binder and a pigment, the dry paint layerhaving an upper surface and a lower surface, a pressure-sensitiveadhesive layer overlying the upper surface of the dry paint layer andadapted for adhering the laminate to a substrate surface at roomtemperature; a release liner overlying the lower surface of the drypaint layer, the release liner removable from the dry paint layer atroom temperature for exposing an outer surface of the dry paint layerwhen the pressure-sensitive adhesive layer adheres the laminate to thesubstrate surface under application of pressure and the release liner ispeeled away from the dry paint layer; and a barrier layer formed as athin, flexible barrier film disposed between the adhesive layer and thecolor layer, the barrier layer film positioned between the adhesivelayer and the color layer and made from a material having a glasstransition temperature greater than about 60° C. so as to inhibitmigration of discoloration-causing pigments from a painted surface ofthe substrate through the adhesive layer to the color layer, in whichthe barrier material has a dry film thickness of not more than about 10%of the total thickness of the decorative laminate (exclusive of therelease liner).
 14. The article according to claim 13 in which thebarrier layer is applied at a dry film thickness in the range of about0.05 to about 0.20 mil.
 15. The article according to claim 13 in whichthe barrier layer comprises an acrylic resinous material which has beencross-linked to an amount sufficient to reduce the pigment transmissionto the color layer.
 16. The article according to claim 13 in which thebarrier layer material includes an adhesion promoter.
 17. The articleaccording to claim 13 in which the laminate further includes a tie coatfor enhancing adhesion between the cross-linked barrier layer and thepressure-sensitive adhesive layer.
 18. The article according to claim 13in which the barrier layer material comprises a high molecular weightacrylic resinous material having a molecular weight in excess of250,000.
 19. The article according to claim 13 in which the barrierlayer material contains a fine particulate dispersed filler materialthat reduces the pigment transmission to the color layer.
 20. Thearticle according to claim 19 in which the barrier filler materialcomprises a metal oxide, a metal compound and/or a melt salt.
 21. Thearticle according to claim 13 in which the pressure-sensitive adhesivecomprises a cross-linked acrylic resinous material.
 22. The articleaccording to claim 13 in which the barrier layer material produces acolor shift of less than about 0.30 Δb* C.I.E. color scale shift unitsat 60° C.
 23. A multi-layer decorative laminate for applying a layer ofcolor to a substrate surface, the laminate comprising: a dry paint layercomprising a color layer which includes a binder and a pigment, the drypaint layer having an upper surface and a lower surface, apressure-sensitive adhesive layer overlying the upper surface of the drypaint layer and adapted for adhering the laminate to a substrate surfaceat room temperature; a release liner overlying the lower surface of thedry paint layer, the release liner removable from the dry paint layer atroom temperature for exposing an outer surface of the dry paint layerwhen the pressure-sensitive adhesive layer adheres the laminate to thesubstrate surface under application of pressure and the release liner ispeeled away from the dry paint layer; and a barrier layer formed as athin, flexible barrier film disposed between the adhesive layer and thecolor layer, the barrier layer film positioned between the adhesivelayer and the color layer and made from a material comprising an acrylicresinous material and a fine particulate additive comprising a metalcompound, a metal oxide and/or a metal salt dispersed in the acrylicresinous material in an amount that reduces migration of or capturesmigrating discoloration-causing pigments from a painted surface of thesubstrate through the adhesive layer to the color layer, in which thebarrier layer material produces a color shift of less than about 0.30Δb* C.I.E. color scale shift units at 60° C.
 24. The article accordingto claim 23 in which the barrier layer is applied at a dry filmthickness in the range of about 0.05 to about 0.20 mil.
 25. The articleaccording to claim 23 in which the barrier layer has a glass transitiontemperature (Tg) greater than about 160° C.
 26. The article according toclaim 23 in which the barrier material has a dry film thickness of notmore than about 10% of the total thickness of the decorative laminate(exclusive of the release liner).
 27. A self-wound multi-layer laminatefor applying a layer of color to a substrate surface, the laminatecomprising: a dry paint layer comprising a color layer which includes abinder and a pigment, the dry paint layer having an upper surface and alower surface, a pressure-sensitive adhesive layer overlying the uppersurface of the dry paint layer and adapted for adhering the laminate toa substrate surface at room temperature; a release liner overlying thelower surface of the dry paint layer, the release liner having a matterelease coat releasably adhered to the lower surface of the dry paintlayer, and an adhesive release coat layer on a side of the release lineropposite from the dry paint layer, the release liner and the matterelease coat removable from the dry paint layer at room temperature, thematte release coat transferring a matte finish to an exposed surface ofthe dry paint layer when the pressure-sensitive adhesive layer adheresthe laminate to the substrate surface under application of pressure andthe release liner is peeled away from the dry paint layer, the laminateadapted for being self-wound into a roll with the pressure-sensitiveadhesive layer in contact with the adhesive release coat layer, theadhesive release coat layer and the pressure-sensitive adhesive layerhaving an unwind release force between them which is lower that acarrier release force between the matte release coat and the dry paintlayer, such that the adhesive release coat preferentially releases theliner from contact with the pressure-sensitive adhesive layer whenunwinding the laminate from its roll form, while the matte release coatmaintains contact with the dry paint layer when the laminate is beingunwound from its roll form, and a barrier layer disposed between theadhesive layer and the color layer and made from a material thatinhibits migration of discoloration-causing pigments from a paintedsurface to which the adhesive side of the laminate is adhered, thebarrier material made of a composition adapted to essentially preventnoticeable color change caused by the migrating pigments from occurringin the color layer under room temperature conditions, in which thebarrier layer material is selected from the group consisting of anacrylic resinous material which has been cross-linked to an amountsufficient to reduce pigment transmission to the color layer, apolymeric material containing an adhesion promoter, a high molecularweight acrylic resinous material having a molecular weight in excess of250,000, or a polymeric material containing a fine particulate dispersedbarrier filler material that reduces pigment transmission to the colorlayer, the barrier filler material comprising a metal oxide, a metalcompound and/or a metal salt.
 28. The article according to claim 27 inwhich the barrier layer is applied at a dry film thickness in the rangeof about 0.05 to about 0.20 mil.
 29. The article according to claim 27in which the barrier layer has a glass transition temperature (Tg)greater than about 160° C.
 30. The article according to claim 27 inwhich the barrier material has a dry film thickness of not more thanabout 10% of the total thickness of the decorative laminate (exclusiveof the release liner).
 31. The article according to claim 27 in whichthe laminate further includes a tie coat for enhancing adhesion betweenthe cross-linked barrier layer and the pressure-sensitive adhesivelayer.
 32. The article according to claim 27 in which the barrier layermaterial produces a color shift of less than about 0.30 Δb* C.I.E. colorscale shift units at 60° C.
 33. A process for making a multi-layerdecorative laminate for applying a layer of color to a substratesurface, the process comprising: forming a dry paint layer on a releaseliner, the dry paint layer comprising a color layer which includes abinder and a pigment, the dry paint layer having an upper surface and alower surface, applying a pressure-sensitive adhesive layer to the uppersurface of the dry paint layer, the adhesive layer adapted for adheringthe laminate to a substrate surface at room temperature; the releaseliner overlying the lower surface of the dry paint layer, the releaseliner removable from the dry paint layer at room temperature forexposing an outer surface of the dry paint layer when thepressure-sensitive adhesive layer adheres the laminate to the substratesurface under application of pressure and the release liner is peeledaway from the dry paint layer; and applying a barrier layer between theadhesive layer and the color layer, the barrier layer formed as a thin,flexible barrier film positioned between the adhesive layer and thecolor layer and made from a material so as to inhibit migration ofdiscoloration-causing pigments from a painted surface of the substratethrough the adhesive layer to the color layer sufficiently toessentially prevent noticeable color change caused by the migratingpigments from occurring in the color layer under room temperatureconditions, in which the barrier layer material is selected from thegroup consisting of an acrylic resinous material which has beencross-linked to an amount sufficient to reduce pigment transmission tothe color layer, a polymeric material containing an adhesion promoter, ahigh molecular weight acrylic resinous material having a molecularweight in excess of 250,000, or a polymeric material containing a fineparticulate dispersed barrier filler material that reduces pigmenttransmission to the color layer, the barrier filler material comprisinga metal oxide, a metal compound and/or a metal salt.
 34. The processaccording to claim 33 in which the barrier layer is applied at a dryfilm thickness in the range of about 0.05 to about 0.20 mil.
 35. Theprocess according to claim 33 in which the barrier layer has a glasstransition temperature (Tg) greater than about 160° C.
 36. The articleaccording to claim 33 in which the barrier material is applied at a dryfilm thickness of not more than about 10% of the total thickness of thedecorative laminate (exclusive of the release liner).
 37. The processaccording to claim 33 including applying a tie coat for improvingadhesion between the cross-linked barrier layer and thepressure-sensitive adhesive layer.
 38. The process according to claim 33in which the barrier layer material produces a color shift of less thanabout 0.30 Δb* C.I.E. color shift units at 60° C.
 39. A multi-layerdecorative laminate for applying a layer of color to a substratesurface, the laminate comprising: a dry paint layer comprising a colorlayer which includes a binder and a pigment, the dry paint layer havingan upper surface and a lower surface, a pressure-sensitive adhesivelayer overlying the upper surface of the dry paint layer and adapted foradhering the laminate to a substrate surface at room temperature; arelease liner overlying the lower surface of the dry paint layer, therelease liner removable from the dry paint layer at room temperature forexposing an outer surface of the dry paint layer when thepressure-sensitive adhesive layer adheres the laminate to the substratesurface under application of pressure and the release liner is peeledaway from the dry paint layer; and a barrier layer formed as a thin,flexible barrier film disposed between the adhesive layer and the colorlayer, the barrier layer film positioned between the adhesive layer andthe color layer and made from a material so as to inhibit migration ofdiscoloration-causing pigments from a painted surface of the substratethrough the adhesive layer to the color layer, the barrier layercomprising one or more of (a)-(c): (a) a material having a glasstransition temperature greater than about 60° C., (b) a material havinga dry film thickness of not more than about 10% of the total thicknessof the decorative laminate, (c) a material that produces a color shiftof less than about 0.30 Δb* C.I.E. color scale shift units at 60° C. 40.A multi-layer decorative laminate for applying a layer of color to asubstrate surface, the laminate comprising: a dry paint layer comprisinga color layer which includes a binder and a pigment, the dry paint layerhaving an upper surface and a lower surface, a pressure-sensitiveadhesive layer overlying the upper surface of the dry paint layer andadapted for adhering the laminate to a substrate surface at roomtemperature; a release liner overlying the lower surface of the drypaint layer, the release liner removable from the dry paint layer atroom temperature for exposing an outer surface of the dry paint layerwhen the pressure-sensitive adhesive layer adheres the laminate to thesubstrate surface under application of pressure and the release liner ispeeled away from the dry paint layer; and a barrier layer formed as athin, flexible barrier film disposed between the adhesive layer and thecolor layer, the barrier layer film positioned between the adhesivelayer and the color layer and made from a material so as to inhibitmigration of discoloration-causing pigments from a painted surface ofthe substrate through the adhesive layer to the color layer, in whichthe laminate further includes one or more of (a)-(b): (a) a tie coat forenhancing adhesion between the barrier layer film and thepressure-sensitive adhesive layer, (b) an adhesive release coat layer ona side of the release liner opposite from the dry paint layer.